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A METHOD 


FOR THE 


Identification of Pure Organic Compounds 


By a Systematic Analytical Procedure Based on Physical 
Properties and Chemical Reactions 


By SAMUEL P. MULLIKEN, Pa.D. 


Associate Professor of Organic Chemical Research, Massachusetts 
Institute of Technology 


Vol. I contains Classified Descriptions of about 2300 of the 
more important Compounds of Carbon with Hydrogen and with 
Hydrogen and Oxygen. 


Large 8vo, xlii+264 pages. Cloth, $5.00 net 


Vol. II, containing Classified Descriptions of themore Impor- 
tant Compounds of Carbon with the Elements Nitrogen, Hydro- 
gen, and Oxygen, Exclusive of the Dyestuffs. 


Price, $5.00 net 


Vol. III, which contained descriptions of the pre-war brands of 
**Commercial Dyestuffs,” is no longer on gale. 


Vol. IV, appearing during the year 1922, contains Classified 
Descriptions of about 3700 of the more important Compounds of 
the ‘‘ Higher Orders.’’ It deals chiefly with the Identification of 
the Organic Halogen and Sulphur Compounds, 


Price, $6.00 net 





A METHOD 


FOR 


THE IDENTIFICATION OF PURE 
ORGANIC COMPOUNDS 


foomor ole NMATIC ANALYTICAL PROCEDURE BASED 
See Pry SICAL sPROPERLIES AND 
Sie MICAL SR EAGIIONS 


Wiley rol | 


CONTAINING CLASSIFIED DESCRIPTIONS 
OF ABOUT 2300 OF THE MORE IMPORTANT COMPOUNDS OF CARBON 
WITH HYDROGEN AND WITH HYDROGEN AND OXYGEN 


BY 


Senne PARSONS ~ MULELEIKEN, “Pie b: 


Associate Professor of Organic Chemical Research at the Massachusetts Institute of Technology, 
Boston, Mass, 


FIRST EDITION 
TOTAL ISSUE, FOUR THOUSAND 


NEW YORK 
JOHN WILEY & SONS, Inc. 
Lonpon: CHAPMAN & HALL, Limitep 


THE GETTY RESEARCH 
INSTITUTE LIBRARY 





= » r “ § ' i ft cae | 
ee aoe are Copyright, 1904, 
q in rat li oe * BY 
SAMUEL PARSONS MULLIKEN 
Entered at Stationers’ Hall. 


bare a 
LAST 2 Ud ee ee 


ie j ve ee 

er! at Sire ‘ (ete 

ii ~ eee 1 press oF) Pate 
Oe A) Foe ee BRAUNWORTH & CO. 


5/22 as | BOOK MANUFACTURERS, =~ 
7 CHT 


4a” yh " . 4 BROOKLYN; Ne'Ys © > © ° 2 . 





PREFACE. 


At the time of writing the only general and fairly systematic procedure for 
vhe identification of previously described organic compounds of all classes is that 
which may be conveniently designated the Method of the Empirical Formula, 
Jn following this procedure a determination of the percentage composition is first 
made. The molecular weight is next determined or conjectured. From these 
data an empirical formula is calculated. The properties of the substance are then 
compared with those of all the known compounds possessing this formula by refer- 
ence to their scattered literature, for which Richter’s ‘‘ Lexicon der Kohlenstoff- 
Verbindungen ”’ with its supplements now furnishes a very complete index. Resting, 
as it chiefly does, on the two fundamental properties, percentage composition and 
molecular weight—which alone among the chemical constants can be readily cal- 
culated for every compound in advance of its discovery—it is probable that this 
method will long remain the last resort in all earnest attempts to establish the 
identity of compounds which have been previously undescribed or very imper- 
fectly characterized through their physical and chemical properties. Nevertheless, 
when we turn to the great body of well-characterized compounds that occur with 
some frequency in the products of Nature, the useful arts, and the scientific labo- 
ratory, there is good reason to raise the question whether the Method of the Empir- 
ical Formula is from the practical standpoint a sufficiently satisfactory one. It is 
evidently not if any substitute can be found that will lead the analyst to the same 
results with less expenditure of time and effort, and without requiring unusual 
knowledge or skill on his part; and it is not to be denied that in these respects 
this method makes a very poor showing, ‘The indispensable key to its use is pro- 
ficiency in ultimate organic analysis, whose difficult technique is fully mastered only 
by long practice. The performance of the combustions, which must be made in 
duplicate to secure certainty, is at best a time-consuming operation; and even after 
reliable results have been obtained, it is further necessary, in order to fully identify 
a compound, to resort to a study of its physical properties, chemical behavior, and 
perhaps to a molecular-weight determination. The consequence of this has been 
that the identification of organic compounds by this general method has been practi- 
cally limited to its occasional employment in laboratories devoted to synthetic 
organic research, and that such identifications when attempted elsewhere are usu- 
ally accomplished, often with uncertain results, by the use of disconnected desultory 
tests. Through these considerations, and with the belief that a path of less resist- 
ance could be broken out for the analyst, the writer began more than eight years 


ago the studies whose first results appear in this volume. 
ili 


iv PREFACE 


The present method, as contrasted with that just described, gives fuller recog- 
nition to the important truths that percentage composition and molecular weight 
are merely two among many highly significant characteristics of every compound; 
and that without recourse to them, by the use of the more easily determined prop- 
erties like qualitative elementary composition, color, melting-point, boiling-point, 
solubility, specific gravity, alkali neutralizing power, and chemical behavior 
under prescribed conditions, entirely satisfactory identifications may be made 
—provided a sufficient number of these facts which are at the disposal of the 
systematist are carefully verified and suitably codrdinated in a classified system. 

The new method therefore rests, as will be more fully explained in the intro- 
ductory chapter, upon a classification designed to secure for the carbon compounds 
those advantages which have been already so long enjoyed in Botany and other 
branches of Natural History through the use of systematized descriptions of salient 
characteristics. The compounds, or chemical “species,’’ have been first grouped into 
“orders”? on the basis of their qualitative elementary composition; then into 
‘genera’? (aldehydes, acids, phenols, etc.), usually on the basis of behavior in 
simple chemical tests; and, finally, arranged within each genus according to the 
increasing value of some readily-determined constant like the melting-point or 
boiling-point. The name of each species is followed in the tables by a brief specific 
characterization enumerating some of the simpler properties of the substance that 
have genuine analytical significance, and then, whenever possible, by detailed 
directions for preliminary and corroborative chemical tests which can be performed 
with small quantities of material. 

The phrase ‘‘More Important Compounds” used in the title is unavoidably 
indefinite; but the intention has been to admit all substances to the tables for 
which there is more than a remote chance that they may come into the hands of 
the analyst as unknown compounds. Such a list naturally includes: first, all com- 
pounds that may be isolated in a state of purity and without excessive difficulty 
from materials used in the arts, or from substances which occur somewhat abun- 
dantly in Nature; second, compounds of minor importance which may easily be 
formed in the laboratory as by-products in reactions between substances of more 
common occurrence; third, many rare compounds which have acquired a general 
scientific interest either on account of their properties or as representatives of 
peculiar types. Very few compounds that could be purchased in the market in a 
state of purity have been omitted except through oversight. The most important 
intentional omissions are: substances whose claims to recognition as distinct 
chemical species are not generally accepted; uncrystallizable syrups that cannot be 
distilled without decomposition; the oily and fatty glycerides; those glucosides 
and synthetic sugars of which specimens could not be obtained for examination. 

The claims for admission to this volume of every compound of carbon with 
hydrogen, or with hydrogen and oxygen, that receives mention in the second edi- 
tion of Beilstein’s great ‘‘ Handbuch der organischen Chemie” and in its supple- 
ments issued prior to January, 1902, have been separately passed upon, and about 
2300 selected as deserving mention in the tables. All copied data used in the 
manuscript sent to the publisher have been twice compared with their source by 
the author and once by Dr. Heyward Scudder. 


PREFACE. us 


Obviously the attempt to establish an analytical system of the proposed char- 
acter on any less secure foundation than an extended first-hand study of a very 
large number of representative compounds so selected as to cover all important 
types, would be to invite the fate of ‘‘the foolish man which built his house upon 
the sand”’; for existing descriptions of the reactions of even the most familiar com- 
pounds very rarely state the experimental conditions and phenomena in terms that 
are immediately available for the purposes of a systematic analytical classification. 
The chemical tests that have been relied upon for arranging the chemical species 
in genera are therefore the result of many hundred original experiments made upon 
several hundred compounds in the laboratories of the Massachusetts Institute of 
Technology, the preparations used being supplied for the most part from the valu- 
able Institute collection. Yet in spite of the considerable labor expended in 
this way, since it has been physically impossible to examine personally every species 
described, it would be absurd to deny that some may be wrongly located in the 
classification. ‘To safeguard the analyst as far as possible against errors arising 
from such imperfect descriptions, every reasonable precaution that has suggested 
itself has been taken during the construction of the procedures and tables. The 
names of those compounds whose generic positions have been established by original 
experiments in the author’s laboratory are distinguished from others by being 
preceded by the mark 7, though it is not true that every property ascribed to a sub- 
stance thus marked is necessarily an original or guaranteed datum. Of the ‘num- 
bered specific tests’? it may, however, be said that each one has been performed 
at least several times in accordance with the directions contained in the manu- 
script; that they have all been used on more than one occasion; and that they 
have proved successful in the hands of two or more persons. 

The specific characterizations are all quite brief because the work is intended 
to be used as a compact practical analytical guide and index, and not as a band- 
book of descriptive Organic Chemistry; and because the value of a specific descrip- 
tion to the analyst never increases, beyond a certain point, directly 1n proportion 
to the number of properties and tests included—long descriptions often becoming 
unwieldy and confusing through suggesting too many alternatives of unequal 
merit. 

To obtain all the new material required for these pages single-handed would 
have proved a disheartening labor. The writer’s grateful acknowledgments 
are therefore due to the many friends (most of whom are or have been connected 
with the chemical department of the Massachusetts Institute of Technology) who 
have rendered assistance in the work. Some of the most important contributions 
from this source are recorded in the unpublished ‘‘thesis’’ investigations of the 
writer’s students. Valuable information has thus been furnished by Messrs. A. P. — 
Norris, C. L. M. Pettee, H. M. Loomis, H. Scudder, B. R. Rickards, A. R. 8. Booth, 
J. W. Brown, J. R. Odell, and Misses E. M. Chandler and A. F. Blood. The writer 
has also been ably assisted at different times by Dr. Paul Chapin and Messrs. A. C. 
Davis and Herbert Walker. To his friend, Dr. Heyward Scudder, the author’s 
thanks are however especially due for generous and untiring codperation during 
a considerable part of this undertaking. Many of the best methods, particularly 
among the ‘specific tests,” are the fruits of his research, or have been improved 


vi PREFACE, 


in consequence of his suggestions, while nearly the whole of the manuscript, as 
well as the proof-sheets, have received the benefit of his criticism. It is regretted 
that the necessary practice of omitting, for the sake of simplicity and compact- 
ness in tabulation, those bibliographical references which, while they have aided 
the writer, would: not be of obvious advantage to the analyst, has prevented 
that full acknowledgment of aid from many earlier investigators that would other- 
wise have been gladly rendered. 

In closing, a word should be added in regard to the proposed extension of this 
“Method” to the other organic compounds. It is planned to describe the carbon 
compounds containing nitrogen, or nitrogen and oxygen—exclusive of the dye- 
stuffs—in Vol. II, as Order II of the analytical system. Although the prepara- 
tion of material for Vol. II is quite far advanced, it is probable that Vol. III, 
which is to be devoted to the identification of the organic dyestuffs, will be ready 
for publication first. The completion of the system will then await the prepara- 
tion of a fourth volume to include the remaining “ orders.”’ 

refed wa 20 


MASSACHUSETTS INSTITUTE OF TECHNOLOGY, December, 1903. 


CONTENTS, 


neg 6) csv wiles vee cle vine eh Nias dels ecele wealescevceenspeevaws 

ERENT TONGS 1G, 5s a's ao Ws vag Bll bra Tol etaases ciate wow ou dis A uls'e aba gley a'eivce a eo 
CHAPTER I, 

CLASSIFICATION OF COMPOUNDS AND THE ANALYTICAL PROCEDURE. ..........-2e00¢ 


Explanation of Classification.—Orders, Genera, Divisions, Sections, Species, 1-2. 

General Directions for Examination of Unknown Compounds.—Evidences of Homo- 
geneity; Examination of Physical Characteristics; Determination of Order; 
Determination of Genus; Tabular Summary of Generic Tests; Determina- 
tion of Division and Section; Determination of Species. 3-7. 

Examples illustrating the Analytical Procedure. 7-8. 


CHAPTER Ii. 


IRM oe Sale iy vgs sk bis 4 0.60 wc s biacy Dee wees © ol «GRC vB ohne ves 
Procedure jor Detection of the Elements in Organic Compounds.—Carbon and Ash Con- 
stituents; Sulphur, Nitrogen, and the Halogens; Ignition with Sodium; Sul- 
phur; Nitrogen; Nitrogen and Sulphur together; Pohsphorus; Halogens; 

Iodine; Bromine; Chlorine. 


CHAPTER III. 


reat send. 1s ORD, 1),—ALDEHYDES. .. 66 ecb bench ce seca renetteane 
Generic Characterization.—Generic Test 1; Observations on Test; Aldehyde Char- 
acteristics, 15-16. 
Analytical Tables.—Div. A (Solid Species), 17-18; Div. B (Liquid Species), 19-21. 
Numbered Specific or Semi-specific Aldehyde Tests.—(101)* Compounds reducing 
Tollen’s Reagent; (111) Acetaldehyde; (112) Acrolein; (113) Benzaldehyde; 
(114) Formic Aldehyde; (115) Furfurol. 22-25. 


CHAPTER IV. 


feeceutl qousorp. 1, Orv. I).—CARBOHYDRATES. «6.662 ie ss cee cere erie dees eas 

Generic Characterization.—Generic Test II; Generic Subdivisions; Carbohydrate 
Characteristics. 26-28. 

Analytical Tables—Section 1 (Soluble Species), 29; Section 2 (Insoluble Spe- 
cies), 31. 

Numbered Sectional and Specific Carbohydrate Tests——(201) Osazone Precipita- 
tions; (202) Reduction of Fehling’s Solution; (203) Furfurol; (204) Phloro- 
glucine Reaction; (205) Oxidations to Mucic or Saccharic Acids. 32-34. 





* The numerals in parentheses refer to test numbers—not pages. 


Vil 


9-14 


15-25 


26-34 


Vill CONTENTS. 


CHAPTER V. 


Genus; TTI (Sunorp, I, Orns D-—Actns os os a ols one ce ee ee 

Generic Characterization —Generic Test III; Observations on Test; Acid Charac- 
teristics; Generic Subdivisions. 35-388. 

Analytical Tables.—Div. A, Sec. 1 (Solid Soluble Species), 39; Div. A, Sec. 2 (Solid 
but not Soluble Species), 52; Div. B, Sec. 1 (Liquid Soluble Species), 73; Div. 
B, Sec. 2 (Liquid but not Soluble Species), 75. 

Numbered Specific or Semi-specific Tests —(301) Neutralization Equivalent; (302) 
a-Oxyacids; (303) Acids losing Carbon Dioxide at 200; (304) Unsaturated 
Acids; (305) Esters with characteristic Odors; (306) Metallic Salts; (307) Acid 
Anhydrides of Genus III; (811) Acetic, Propionic, Butyric, and Isobutyric 
Acids; (812) Benzoic Acid; (813) Cinnamic Acid; (314) Citric, Malic, and 
Tartaric Acids; (315) Formic Acid; (316) Glutaric Acid; (317) Oxalie Acid; 
(318) Phthalic Acid, Isophthalic Acid and Terephthalic Acid; (319) Salicylic 
Acid; (820) Succinic Acid. 77-86. 


CHAPTER VI. 


Genus IV (Suporp. I, Orv. I).— PHENOLIC COMPOUNDS... .....ccccccccvccceccces 4 

Generic Characterization.—Generic Test IV. Observations on Test; Phenolic Char- 
acteristics. 87-90. 

Analytical Tables.—Div. A (Solid Species), 91; Div. B (Liquid Species), 104. 

Numbered Specific or Semi-specific Tests——(401) Ferric-chloride Colorations; 
(402) Phthaleine Fusion; (411) Hydroquinone; (412) a-Naphthol; (413) 
68-Naphthol; (414) Phenol; (415) Phloroglucine; (416) Pyrocatechin; (417) 
Pyrogallol; (418) Resorcine; (419) Thymol. 107-110. 


CHAPTER VII. 


Genus V (SunorpD. I, Ornp. I1)—-ESTEeRs ......... sep eves +s+eee ces one 
Generic Characterization.—Generic Test V, 111; Saponification and Saponification 
Equivalent (Rapid Method), 111; Saponification to obtain both Acid and 
Neutral Products (Longer Method), 113; Examination of the most Important 
Neutral Saponification Products, 113; Examination of the Acid Products, 
116; Observations on Test V. 117. 
Analytical Tables —Div. A (Solid Esters), 118; Div. B (Liquid Esters), 120. 


CHAPTER VIII. 


Genus VI (Suporp. I, Orv. J).—Acip ANHYDRIDES AND LACTONES...........cee0e 
Generic Characterization, 128. 
Analytical Tables.—Div. A (Solid Species), 129; Div. B (Liquid. Species), 131. 


CHAPTER IX. 


Genus VIL (Suporp. I, Orv. 1).—KETONES.. . 2... 52, Daa ce ele ce 

Generic Characterization.—Generic Test VII; Procedures 1 and 2; Observations 
on the Test. 133-135. 

Analytical Tables—Div. A (Solid Species), 136; Div. B (Liquid Species), 141. 

Numbered Specific or Semi-specific Ketone Tests —(701) Colorations with Sodium 
Nitroprusside; (702) Oxidations with Chromic Acid; (703) Pyrrol-red Reaction 
of 7-Diketones; (711) Acetone; (712) Acetophenone; (713) Benzoin; (714) 
Benzophenone; (715) Camphor. 146-150. 


87-110 


111-127 


128-132 


133-150 


CONTENTS. ix 


CHAPTER X. 


Meee tiles BoRD. I, Ord. [).—ALCOHOLS .....0..00.. ccc cceccccncvemeccuccees 151-172 

Generic Characterization.—Generic Test VIII; Procedures 1, 2, and 3; Observations 
on the Test. 151-154. 

Analytical Tables—Div. A, Sec. 1 (Solid ‘‘Soluble” Species), 155; Div. A, Sec. 2 
(Solid and not ‘‘Soluble” Species), 158; Div. B (Liquid Species), with Sp. Gr. 
less than 0.90), 160; Div. B, Sec. 2 (Liquid Species, with Sp. Gr. greater than 
0.90), 164. 

Numbered Specific or Semi-specific Tests —(801) The Iodoform Test; (811) Allyl 
Aleohol; (812) Benzyl Alcohol; (813) Butyl Alcohol; (814) Ethyl Alcohol; 
(815) Ethylene Glycol; (816) Glycerine; (817) Isobutyl Alcohol; (818) Iso- 
propyl Alcohol; (819) Methyl Alcohol; (820) Propyl Alcohol. 166-72. 


CHAPTER XI. 


Grnus IX (SusBorp. I, Orp. I) HYDROCARBONS, ETC ...........ce cece cccees ee eh 7o-2U3 
Generic Characterization, and the Sectional Tests, 173. 
Analytical Tables—Div. A (Solid Species), 174; Div. B, Sec. 1 (Liquid Species. 

Sp. Gr. below 0.85, not giving Tests 901-903), 182; Div. B, Sec. 2 (Liquid Spe- 
cies, Sp. Gr. below 0.85, but attacked in Tests 901, 902, or 903), 184; Div. B, 
Sec. 3 (Liquid Species, Sp. Gr. above 0.85), 189. 

Numbered Specific or Semi-specific Tests —(901) Bromine Test for Unsaturation, 
etc.; (902) Action of Fuming Sulphuric Acid; (903) Action of Fuming Nitric 
Acid; (904) Colorations with Aluminium Chloride; (905) Oxidation of Side- 
chains (1) with Permanganate, (2) with Chromic Acid, (8) with Nitric Acid; 
(906) Test for C:CH Group; (907) Saturated Ethers of Div. B; (911) Ace- 
naphthene; (912) Anthracene; (913) Benzene; (914) Mesitylene; (915) 
Naphthalene; (916) Phenanthrene; (917) Pseudocumene; (918) Toluene; 
(919) m-Xylene; (920) p-Xylene; (921) o-Xylene. 195-203. 


CHAPTER XII. 


SUBORDER II oF OrpDER I.—CoLORED COMPOUNDS OF ORDER I...........cc cece ecces 204-216 
Subordinal Characterization, 204. 
Analytical Tables.—Div. A, Sec. 1 (Solid Species of Determined Melting-point), 205; 
Div. A (Supplementary), Sec. 2, 212; Div. B (Liquid Species), 215. 
Numbered Specific Tests —No. 1011, Anthraquinone; 1012, Benzoquinone; 1013, 
a-Naphthoquinone; 1014, Phenanthrenequinone, 216. 


CHAPTER XIII. 


Seat) METHODS, APPARATUS, AND RWAGENTS. .....2..s000sccsscervnseecesenncss 217-237 

Melting- and Boiling-points—Usual and Special Methods for Determining; Sources 
of Error and Corrections, 217-223. 

Thermometric Indications of Chemical Purity —Fractionation Tests; Sharpness Tests; 
Fusion and Boiling Intervals. 223-227. 

Specific Gravities—Determination with the Capillary Pyne or the Pipette, 
227-229. 

Color.—Color Terminology; Pigmentary Color Standards; Color Symbols; Color 
Comparisons, 230-234. 


List of Special Reagents and Apparatus, 236-237, 





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ald. 
alm. 
alk. 
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aq. 
as. 
b. p. 
Bu. 


d. a. 


d.w.m. 
delig. 
dil. 


TABLE OF ABBREVIATIONS. 


=above. Before a melting-point or 
boiling-point indicates that the 
change occurs above the tem- 
perature given. 
=about. Indicates that the value 
following is only approximate. 
(standing after the symbol for a 
metal)represents the acid residue 
of the acid in whose description 
it occurs; e.g., PbA, in a descrip- 
tion of benzoic acid would rep- 
resent lead benzoate. 
= acetic acid or acetate. 
=acid. 
= alcohol or alcoholic. 
= aldehyde. 
= almost. 
= alkaline. 
= anhydride. 
= water or aqueous. 
=asymmetrical. 
= boiling-point. 
=butyl, C,H,, without regard to 
structure of the radical. 
= benzene. 
=corrected (not necessarily correct) ; 
also cold. 
= chloroform. 
= concentrated. 
=crystals, crystalline, or crystallizes. 
=decomposes. Standing after a 
number indicates the tempera- 
ture at which a substance melts 
or boils with decomposition. 
Standing before a number it indi- 
cates the temperature at which 
decomposition occurs without 
necessarily implying that the 
substance either melts or boils. 
Standing before the name of a 
compound means dextro-gyra- 
tory. 
=decomposes above. Is used in the 
same way as d. 
= decomposes without melting. 
=deliquescent or deliquesces. 
=dilute. In expressions like ‘dil. 
ale. (8:1),” the first term of the 
numerical ratio between paren- 
theses always refers to the sub- 
stance directly mentioned, and 
the second term to the water 
used as diluent or solvent. 
= difference. 
=distils; also, may be distilled, 
without stating the tempera- 


ture. 
=difficultly soluble. See page 38. 
=ethyl, C,H;,. 
=ether, (ethyl oxide). 
=easily soluble. See page 38. 





Tr. 
floc. 


sol. 


Sef 


Sbl. w. m. =sublimes without melting. 


tbl. 


(Th. i.) 


volat. 


vol. w. st. 


wW. 
Zz. &. 


=from. 

= flocculent. 

= hot. 

= insoluble; also, in name of a com- 
pound, optically inactive. 

=in vacuo. 

= specific gravity. 

= granular. 


- =levo-qyratory. 


= | qu id. 

=ligroin. 

= meta. 

= microscopic. 

= methyl, CH. 

= miscible. 

= melting-point. 

= ‘neutralization equivalent.” 

fined on page 77.) 

=non-fusible. 

= non-volatile. 

= ortho. 

=ordinary atmospheric pressure. 
=ordinary room temperature. 
=oridize, oxidizes, or oxidation. 
= para. 

=pnenyl, C.Hs. 
= propyl, C,H, (without indicating 

the structure of the radical). 

= precipitate or precipitates. 
= part or parts. 


(De« 


= pulverulent. 
=rapidly heated. (See page 220.) 
=soluble. (See page 38.)—Before 


the name of a compound signi- 
fies symmetrical. 

= sublimes. 

= slightly decomposed. (Signifies that 
the substances melts or boils 
with slight decomposition at the 
temperature given.) 


= saponification equivalent. (Defined 


on page 113.) 
= solution. 
=softens. Indicates that the sub- 
stance softens at the tempera- 
ture stated. 
(Often 


followed by specification of the 
temperature.) 

=tabular crystals. 

= thermometer immersed in the vapor. 

= uncorrected. 

= unsaturated. 

=vicinal or adjacent. 

= volume. 

= volatile. 

= volatile with steam. 

=with. 

= €XCESS. 


xil SIGNS.—BIBLIOGRAPHICAL. 


SIGNS. 


[e]p Specific rotary power (using monochromatic sodium fight). For the carbohy- 
drates the values given are the ‘‘permanent” rotations at 20° C. obtained 
with aqueous solutions. 

[y]p Index of refraction (using monochromatic sodium light). 

“+ placed after a number in a column of boiling- or melting-points indicates that the 
substance melts or boils slightly above the temperature given. 

{[+]lor[—] placed before the name or symbol for a compound indicates that the substance is 
optically active. 

T placed before the name of a compound indicates that the position of the latter in 
the analytical system has been experimentally determined in the author’s 
laboratory. ‘The “specific descriptions” for such compounds are also based, 
for the most part, on experimentally verified data. 





BIBLIOGRAPHICAL. 
Abbreviation. Title. 
A. Liebig’s Annalen der Chemie. 
A. ch. Annales de chimie et de physique. 
A. ch. an. Annales de chimie analytique. 
Allen. Allen’s Commercial Organic Analysis, 3d Edition (Blackiston’s Son). 
Anl. The Analyst. 
Am. American Chemical Journal. 
Am. Soe. Journal of the American Chemical Society. 
Ar. Archiv der Pharmacie. 
B. Berichte der deutschen chemischen Gesellschaft. 
BL. Bulletin de la Société Chimique de Paris. 
C. Chemisches Centralblatt. 
Orr: Comptes rendus de |’ Académie des Sciences. 
Ch. Ind. Journal of the Society of Chemical Industry. 
Ch, Z. Chemiker Zeitung (Céthen). 
Cho N; Chemical Nevs. 
rT. (Fresenius’) Zeitschrift fiir analytische Chemie. 
G. Gazzetta Chimica italiana. 
lee (Hoppe-Seyler’s) Zeitschrift fir physiologische Chemie. 
J. Jahresbericht der Chemie. 
Jape: Journal fiir praktische Chemie. 
M. Monatshefte fur Chemic. 
Ph. Ch. Zeitschrift fiir physicalische Chemie. 
R Recucil des travaux chimiques des Pays-Bas. 


Soc. Journal of the Chemical Society of London. 


re see eee eee eee ee ee ee TT TT ee ee a EL ELLE LEE ELLE I SELL TCE IE) 


IDENTIFICATION OF ORGANIC COMPOUNDS. 


CHAPTER I. 


CLASSIFICATION OF COMPOUNDS AND THE GENERAL 
ANALYTICAL PROCEDURE. 


To facilitate their identification, the pure compounds or chemical species 
described in this work are systematically arranged in genera, orders, and various 
minor groups. The general analytical procedure can be applied intelligently only 
after the underlying principles of this classification are clearly understood. 

The order of any species is determined by its qualitative elementary compo- 
sition. Compounds made up of the same elements belong to the same order. The 
compounds of carbon and hydrogen, and of carbon, hydrogen, and oxygen, con- 
stitute Order I of the system, and are the only ones described in the present volume. 
Order I contains two suborders, Suborder I including all colorless, and Suborder IT 
all colored species. Tests having as their object the determination of the order of a 
species, i.e. tests for the elements, are called ordinal tests. ‘They will be fully treated 
in Chapter IT. . 

A genus is a group of species characterized by showing a common behavior in 
certain prescribed and carefully defined generic tests. With few exceptions generic 
tests are based on chemical reactions rather than differences in physical properties. 
The experimental details for each generic test are to be found at the beginning 
of the chapter devoted to the genus whose number it bears. Typographically 
generic tests are distinguished from other numbered tests by being printed in Roman 
instead of Arabic numerals. Test III, for instance, means the test prescribed 
(page 35) for the recognition of species of Genus III (Acids). The genera are so 
arranged that no species shall give the generic test for any genus preceding it in 
the same suborder. A concise summary of the generic tests of Suborder I, Order I, 
is given on page 5. 

All genera, including both solid and liquid species, contain two divisions. 
Division A contains the solid, and Division B the fluid species. Gaseous species 
are so few in number that they are treated in division B with the species that are 
liquid under the ordinary conditions of temperature and pressure. 

The “ divisions”’ of some genera are composed of smaller groups of species called 
sections. The term section is also, though less frequently, applied to small arti- 
ficial groups of species, like the two sections of Suborder II, when the chemical 


2 CLASSIFICATION OF COMPOUNDS. 


relationships between the members of the group are not sufficiently intimate to 
warrant their erection into genera. Sectional tests when based upon chemical 
reactions are referred to by numbers, and described just before the true specific 
tests, and immediately after the tabulated descriptions of the species of the genus. 

The chemical species or compounds, the fundamental units in the classification, 
are, whenever practicable, arranged within their respective genera, divisions, or 
sections according to the numerical values of their melting-points, if they are 
solids; or of their boiling-points, under standard conditions, if they are liquids. 
Genus II of Suborder I, and Supplementary Section 2 of Suborder IJ, furnish the 
only examples in this volume, of groups of compounds whose arrangement within 
their respective sections of the tables is not dependent on the values of these 
constants. 

Specific tests are primarily designed to distinguish a species from others situated 
near it in the same subdivision of its genus, and in the regular course of analysis 
should follow the ordinal, generic, and sectional tests. Very few of them have much — 
significance if applied directly to an entirely unknown compound. It is conceivable, 
for instance, that there may be a number of organic liquids which will give a white 
crystalline derivative melting at 92°-93° when treated as directed in Specific Test 
814; but if it is also shown that the unknown substance is a colorless compound 
of carbon, hydrogen, and oxygen belonging to Genus VIII, Division 2, and boiling 
at 78°, the proof that the species is ethyl alcohol is overwhelming. ‘The most satis- 
factory specific tests are usually those in which a few centigrams of a compound 
are quickly converted into a well-characterized derivative. 

The directions for many specific tests form a part of the specific characterizations 
of the tables, but some of the more important tests in each genus are described 
together immediately after the tables of the genus to which they relate, and referred 
to in the characterization by test numbers. In Order I, one hundred numbers are 
reserved for the description of the sectional, semi-specific, and specific tests of each 
- genus, the first ten numbers in each hundred being set aside for the sectional and 
semi-specific,* and the last ninety for the true specific tests. Any numbered test 
in Order I may be easily found without consulting the index, if it be remembered 
that the numeral denoting the hundreds in the test number (e.g. 3 in 321) is also 
the number of the genus to which the compound concerned in the test belongs. 
The last two numerals in the test number indicate the position of the test among 
its fellows. Test 302 will accordingly be recognized at a glance as either a sec- 
tional or semi-specific test of Genus III (Acids). By turning to page 78 
it will be found to be a reaction for the recognition of a-hydroxy acids. In 
the same way Test 319 will be seen to be a specific test for some particular acid. 
It is actually a description of two reactions for the identification of salicylic acid. 
The tests connected with the nine genera of Suborder I, Order I, are assigned 
numbers 100-900. Suborder II, not being divided into genera, has its specific 
tests numbered as if it were the tenth genus of its order; i.e. they are represented. 
by the numbers 1000 to 1100. . Soe 4 


* By a semi-specific test is meant one employing some general experimental procedure 
that leads to similar results with a number of compounds, but which enables a partial selec- 
tion between some of the species situated in the same smallest subdivi ision of a genus. ae 
301, 302, and 303 are semi-specific tests. ‘ : aie 


GENERAL ANALYTICAL PROCEDURE. 3 


GENERAL DIRECTIONS FOR THE IDENTIFICATION OF AN UNKNOWN 
COMPOUND. 


The numbered paragraphs in heavy type which follow form an analytical 
key to the use of the “ Method”. They indicate the successive considerations that 
should receive the attention of the analyst in the investigation of every unknown 
compound. With the explanatory remarks in ordinary type which accompany 
them, they give a comprehensive view of the general analytical procedure disen- 
cumbered of detailed descriptions of special operations and tests which can be 
more advantageously discussed elsewhere. It will be assumed that the reader has 
already acquainted himself with the classification of the ‘‘ Method ”’. 


I. PURITY. 


ESTABLISH A PRESUMPTION THAT THE UNKNOWN SUBSTANCE IS REALLY A PURE 
COMPOUND BEFORE ATTEMPTING TO IDENTIFY IT. IF IT IS NOT HOMOGE- 
NEOUS, PURIFY IT. THE CONSTITUENTS OF AN UNKNOWN ORGANIC MIXTURE 
CAN NOT BE SATISFACTORILY IDENTIFIED PREVIOUS TO THEIR SEPARATION. 
THE HOMOGENEITY OF COMPOUNDS WHICH EXIST ONLY IN THE FORM OF 
UNCRYSTALLIZABLE SYRUPS THAT CAN NOT BE DISTILLED WITHOUT SERI- 
OUS DECOMPOSITION, IS SO DIFFICULT TO ESTABLISH, THAT SUCH SPECIES 
ARE, AS A RULE, EXCLUDED FROM THE TABLES. 

To prove absolutely that a substance is chemically homogeneous, it would have to 
be shown that the physical and chemical properties of all the parts into which a given 
mass of it can be separated by methods of fractionation that do not affect it chemically, 
are identical; or, in other words, that no substance can be thus isolated from it whose 
melting-point, boiling-point, solubility, specific gravity, crystalline structure, chemical 
behavior, etc., is different from that of the original body. This absolute proof is of course 
impossible in practice. But if the properties whose identity in the several fractions has 
been ascertained are very few in number, they may still afford a presumption in favor 
of chemical homogeneity so strong as to closely approximate to the absolute proof, pro- 
vided they are judiciously selected and are of a kind that permit of exact measurement. 

The decision of the analyst as to just how many and what purity tests it will be profit- 
able to apply to any particular substance, will be influenced by a variety of circumstances, 
among which will be included the importance of the identification, the extent of his knowl- 
edge of the methods employed in the preparation and purification of the substance, and 
the quantity of material that is available. If the supply is so small as to barely suffice 
for the tests of the regular procedure exclusive of special homogeneity tests, there will be 
no alternative between abandoning the examination altogether, and hazarding the loss 
of all the substance in what may at the end prove to be fruitless experiments upon a mix- 
ture. Whenever it is decided in such a case to proceed with the examination, it must 
be remembered that the results will be worthless unless the final specific tests are most 
unequivocal. 

Of all the methods affording indications of purity, those which depend upon constancy 
or sharpness in melting- and boiling-point have been the most widely used. Indeed, it is 
altogether probable that for a majority of the organic compounds which have been described, 
the only direct evidence of purity that it has been considered necessary to secure, pre- 
liminary to the first ultimate analysis,—aside from that incidentally gained from their 
general appearance and behavior towards solvents—has been that furnished by these 
simple thermometric methods. The use and interpretation of these purity tests will be 
discussed somewhat fuliy in Chapter XIII (pp. 223-227). 

The truth of the proposition that “The constituents of an unknown mixture can not 
be satisfactorily identified previous to isolation,” may, at the first glance, appear to be 


4 GENERAL ANALYTICAL PROCEDURE 


invalidated by the existence of direct tests for organic adulterants in foods, for abnormal 
constituents in the urine, and the like. These tests, however, all owe their usefulness 
to the fact that the mixtures to which they are applied—except as regards the compound 
sought—are, virtually, known mixtures, in the sense that the combined effect of all their 
customary constituents—known and unknown—upon the test, has been carefully ascer 
tained by previous investigations. Their value accordingly becomes problematical a 
soon as any substance not usually present in such a mixture is added to it. 

The preliminary treatment of unknown mixtures is, undoubtedly, that part of most 
organic analyses which makes the greatest demands on the originality and patience of 
the analyst. While the number and peculiarities in chemical behavior of the organic 
compounds are so great as to forbid the expectation that a general scheme for their separa- 
tion comparable in simplicity and comprehensiveness to that used in qualitative analysis 
for the elements can ever be realized, it is reasonable to anticipate that this important 
branch of Analytical Chemistry will eventually be so far systematized that much less will 
be left to chance and individual dexterity than at present. The omission from this volume 
of suggestions for methods of separation occurs, not because the importance of the matter 
has been underestimated, but because sufficient data for comprehensive and practical 
generalizations on the subject have not yet accumulated. It is, however, the author’s hope 
to present such recommendations as can be given for the systematic treatment of mixtures 
in a later volume. 


2. PHYSICAL PROPERTIES. 


IF THE SUBSTANCE IS A SOLID, DETERMINE ITS MELTING-POINT; IF A LIQUID, ITS 
BOILING-POINT AND ITS SPECIFIC GRAVITY AT 20°/4°. IN EITHER CASE 
NOTE ITS ODOR, COLOR, TASTE, AND OTHER SALIENT PHYSICAL CHARAC- 
TERISTICS, AND DETERMINE ITS APPROXIMATE SOLUBILITY IN WATER. 

The determination of melting-points is discussed on pages 217-221. Most 
of the melting-points recorded in the tables are probably “uncorrected.” The 
boiling-points, on the contrary, are in general to be regarded as corrected for 
stem-exposure, and have been approximately reduced to their values under the 
standard pressure of 760 millimeters whenever possible. The determination of 
boiling-points is treated on pages 221-223. Whenever small distilling flasks 
are employed in making these determinations, the use of the asbestos diaphragm 
shown in Fig. 6 should never be neglected. The specific gravity of liquids, 
if the quantity available is very smail, is best determined by aid of the capillary 

pyknometer described on page 228. 0.2 cc. of the liquid will be enough to enable a 

satisfactory determination in this apparatus. Color comparisons should be expressed 

in terms of the color standard placed in the back cover of this volume and described 
on pages 230-234. The determination of solubility in water at the temperature 

of the laboratory may be quickly made by the approximate method of page 38. 


These tests are made so early in the procedure, because, unlike most of those which 
follow, they consume little or no material which can not be recovered, while the informa- 
tion which they furnish is almost certain to be required at some later period in the inyesti- 
gation. 


3. ORDER. 


DETERMINE THE ORDER OF THE COMPOUND BY APPLYING THE ORDINAL TESTS 
IN THE SUCCESSION AND MANNER DIRECTED IN CHAPTER II, PAGE 9 ET 
SEQ. IF THE COMPOUND CONTAINS ANY ELEMENTS OTHER THAN CARBON, 
HYDROGEN, AND OXYGEN, IT IS NOT DESCRIBED IN THIS VOLUME. IF 
IT CONTAINS CARBON AND HYDROGEN, OR CARBON, HYDROGEN, AND OXY- 
GEN, AND IS COLORLESS, IT BELONGS TO SUBORDER I, ORDER I. _ IN THIS 
CASE TURN TO PARAGRAPH 4 BELOW. _ IF IT BELONGS TO ORDER I, BUT IS 
COLORED (ILE., BELONGS TO SUBORDER II), TURN TO PAGE 204, 


GENERAL ANALYTICAL PROCEDURE. 4) 


4. GENUS. 


{For Species of Suborder I, Order I.}-APPLY GENERIC TESTS I-IX SUCCESSIVELY UNTIL 
THE GENUS OF THE COMPOUND IS ASCERTAINED. DO NOT VARY THE ORDER 
OF THE TESTS, NOR OMIT ANY WHICH ARE NOT KNOWN FROM THE CIRCUM- 
STANCES TO BE POSITIVELY UNNECESSARY. BEFORE PERFORMING ANY 
GENERIC TEST FOR THE FIRST TIME, READ CAREFULLY THE “OBSERVA- 
TIONS’? WHICH FOLLOW THE DIRECTIONS. THE PAGES ON WHICH DIREC- 
TIONS FOR THE SEVERAL GENERIC TESTS ARE TO BE FOUND, ARE GIVEN IN 
THE “TABULAR SUMMARY OF GENERIC TESTS” BELOW. 


When a generic test is subdivided into parts, a statement of the sequence in 
which they should be applied, or of the circumstances under which certain of them 
are to be omitted, is always conspicuously placed near the head of the chapter 
devoted to the genus. 

TABULAR SUMMARY OF GENERIC TESTS I-IX IN SUBORDER I, ORDER I. 





Test_ Number Condensed Description of Test. 
and Page. 
I (p. 15) Aldehydes.—A color reaction with a fuchsine solution decolorized by sulphur- 


ous acid. Requires 5 cgr. of substance. ‘Time about 3 minutes. 


II (p. 26) Carbohydrates——The Molisch color reaction with a-naphthol, followed by 
three short supplementary tests to exclude glucosides in case the proper 
color is obtained. The Molisch reaction requires 5 mgr. of substance and 
can be applied in 5 minutes. The supplementary tests, when made, 
require in all 11 cgr. of substance and can be applied in 5 minutes. 


Ii (p. 35) Acids.—A titration with decinormal sodium hydroxide and phenolphthalein, 
Requires 1 decigr. of substance. Time about 30 minutes when a neutrali- 
zation equivalent is determined; in other cases (cf. note on p. 35) 5 
minutes. 


IV (p. 27) Phenolic Compounds.—The test has two parts: (1) a color test with ferric 
chloride consuming 5 to 10 mgr. of substance, which can be applied in less 
than 5 minutes; (2) a solubility test with aqueous alkali, which can be 
made with 10 cgr. of substance in 4 minutes. Part 2 is used only for 
solids that fail to give part 1. 


V and VI Esters and Anhydrides.—-A saponification experiment with 10 cgr. of substance, 
(pp. 111-128) which is heated with 2 cc. of alcoholic potash solution for 30 minutes. 
(During the heating, preparations for Tests VII and VIII will be made.) 
[A second longer-and more difficult saponification procedure (cf. p.113) with 
aqueous potash and a gram or two of substance is required when it is 
wished to isolate the neutral saponification products from an ester, and 
thus distinguish certainly between species of Genera V and VI. It is 
never applied when the first procedure has given a negative result; and 
its use is generally inadvisable when the total supply of substance does 
not exceed 2 grams. When omitted, Genera V and VI have to be treated 
as a single composite genus. ] 


VII (p. 133) | Ketones.—Solid compounds melting above 30° are tested with hot alkaline 
hydroxylamine solution; all compounds liquid at temperatures below 30°, 
with phenylhydrazine solution. The test with hydroxylamine requires 
10 cgr. of substance; that with phenylhydrazine about 5 cgr. Time in 
either test about 15 minutes. 


VIII (p.151) | Alcohols.—To this genus belong: (A), all species not included in earlier genera 
that are soluble in less than 30 parts of water at 20°; (B), all compounds 
liquid below 75° that evolve hydrogen on treatment with sodium; (C), all 
compounds solid at 75° that are not acetylated by acetic anhydride under 
certain prescribed conditions. Test A has been already made in the pre- 
liminary examination. Tests B and C require about 20 egr. and 10 cgr. 
of substance respectively. Test B can be performed in 10 or 15 minutes; 
C can not be completed in less than about 50 minutes. [In dealing with 
insoluble solids time will often be saved by referring directly to the appro- 
priate division and section in the tables of both Genus VIII and IX with- 
out applying test C.] 

IX (p.173) | Hydrocarbons, etc.—Genus IX includes all species not giving Tests I to IX, 
. and hence has no special generic test of its own, 











6 GENERAL ANALYTICAL PROCEDURE 


5. GENERIC SUBDIVISIONS. 


TURN TO THE PROPER DIVISION (A FOR SOLIDS, AND B FOR LIOUIDS) IN THE 
TABLES OF THE GENUS. IF THE DIVISION CONTAINS SECTIONS, THE DE- 
SCRIPTIVE DIVISIONAL HEADINGS WILL INDICATE WHAT ADDITIONAL TESTS, 
IF ANY ARE NECESSARY, MUST BE MADE TO ASCERTAIN THE SECTION. 

AS the divisions in many genera are not subdivided, and as many of the sections are 
distinguished from one another by differences in solubility or specific gravity which are 
already known from the preliminary examination of paragraph 2, additional tests at this 
point are usually unnecessary. The following table gives a general view of the subdi- 
visions of the genera of Suborder I, together with page numbers oi each divisional heading. 


SUBDIVISIONS OF THE GENERA IN SUBORDER I, ORDER IL. 
ee ee ee 














Genus Page No. Number 
and of Division of Basis of Sectional Distinctions. 
Divisions. ead. Sections. 
Le 17 0 
B 19 0 
iA - 2 Solubility in water at 20°, with special chemical tests for 
III A 39 2 : Pp 
subsections. 
B 73 2.) 
IV A 91 0 
B 104 0 
Alger. 118 0 
B 120 2 
VIA 129 0 
B 131 0 
VII A 135 0 
B 141 0 
VIII A 155 2 Solubility in water at 20°. 
B 160 2 Sp. gr. (20°/4°) greater or less than 0.99. 
IX A 174 0 . 
B 182 3 Sp. gr. (20°/4°) in sections 1 and 2 less than 0.85; in 3 
greater than 0.85. Sec. 1 is distinguished from 2 by 
chemical tests. 


6. SPECIES. 


COMPARE THE PROPERTIES OF THE SUBSTANCE WITH THE PROPERTIES OF ALL 
SPECIES THAT MELT OR BOIL WITHIN FIVE OR TEN DEGREES OF ITS MELT- 
ING- OR BOILING-POINT AND ARE DESCRIBED IN THE SUBDIVISION OF THE 
GENUS TO WHICH IT HAS BEEN FOUND TO BELONG. 


The published data concerning melting- and boiling-points are, unfortunately, 
not always based upon exact determinations. (See page 217.) Hence the necessity 
for extending the inspection of the tables to include species that are described as 
melting or boiling a number of degrees from the temperature actually observed. 
The 5° limit is sufficient for most species whose melting- or boiling-points are below 
150°; but the limit of 10° is none too large for compounds that melt or boil at 300°. 
When the recorded and observed temperatures are both ‘‘ corrected’’ ones, the 
limit may be safely much reduced. The mode of procedure in the few sections: 
in which the species are not arranged according to melting- or boiling-points, will 
always be sufficiently indicated in the sectional headings of the tables. 

The specific characteristics most serviceable in making a first partial choice 
between compounds having nearly the same melting-points or boiling-points arei 
properties like color, taste, and odor, which are obvious from a casual inspection; 
properties like specific gravity, solubility, boiling-point (for solids), refractive 
index, and neutralization equivalent, for which numerical values can be deter- 


GENERAL ANALYTICAL PROCEDURE. td 


mined quickly, or which are already known in consequence of the preliminary 
examination and the generic, divisional, and sectional tests that have been made; 
and, lastly, simple semi-specific tests, such as number 901 with bromine for unsatu- 
ration, or 302 with ferric chloride for a-oxyacids. Undue weight should not be 
attached to statements concerning crystalline form which are unaccompanied by 
exact crystallographic measurements; the general appearance of crystals of the 
same compound being often strongly influenced by the solvent, temperature, and 
other conditions accompanying crystallization. 

The final confirmatory specific tests of the tables are not all of equal merit 
ov conclusiveness. Many which have been inserted on the strength of apparently 
good authority, but not verified by the author, may be deficient in essential details. 
Those introduced by the words ‘‘ Apply Test —” or ‘‘ Identify by Test —” have been 
carefully studied in the author’s laboratory, and may be accepted as thoroughly 
reliable. The basis for the recommendation of such as begin with the phrase ‘‘ Gives 
Test —’ or ‘‘ Gives —in Test —” (e.g. ‘‘ Gives isophthalic acid in Test 905”’) is either 
experiments made in the author’s laboratory, or positive published statements 
that the result specified has been produced under conditions which it is reasonably 
certain will be supplied by the method of the numbered test cited. 

To complete the identification of any compound for which adequate specific 
confirmatory tests are not suggested in the tables, recourse to the original litera- 
ture of the body and its derivatives will frequently be necessary. These descrip- 
tions have now been made so accessible, and are so well summarized in “ Beilstein’s 
Handbuch ”’, that suggestions for the desired tests will often be quite readily found. 
Some general remarks on the selection of suitable derivatives for use in such 
impromptu specific tests are given on page 234. 

The properties of many of the species whose names appear in the chemical literature 
have, however, been either so imperfectly determined or described, that their identifica- 
tion by any purely analytical method, without some knowledge of the reactions leading 
to their formation, is an impossibility. All that can be done analytically with such com- 
pounds, when the quantity of material is limited, is to ascertain whether their percentage 
compositions and molecular weights harmonize with any hypothesis that we may be in a 
position to make concerning them. In such cases it will usually make little difference 
whether we begin or close the examination of the body with the determination of an em-. 
pirical formula; for when all has been done that is possible under the circumstances, the 
labor performed will be the same, whichever procedure is chosen. Substantial justifica- 
tion for the subordination of the method of identification by properties and reactions 
to that founded on the empirical formula, exists in one case only. This is met with when 
there are strong reasons for suspecting the unknown substance to be a new compound, 
or one very unlikely to appear in the tables of this work, and when its quantity is less 
than about two grams. It would then be unfortunate, in view of the anticipated failure of 
the attempt at identification by properties and reactions, to forego the possible advan- 
tages that might be derived from a knowledge of the empirical formula. 


EXAMPLES ILLUSTRATING THE ANALYTICAL PROCEDURE. 


The following examples of identifications by the procedure of this “Method” are 
the records of actual experiments made in a laboratory where the apparatus and reagents 
required were all in readiness. The contents of each numbered paragraph are a record 
of the results obtained by following that part of “General Directions for the Identification 


8 ILLUSTRATIVE EXAMPLES. 


of an Unknown Compound” summarized in the paragraph in heavy type designated by the 
same number. The compounds being known to be pure, the description of operations 
begins with the examination of physical properties referred to in paragraph “‘(2),” page 4, 
of the ‘‘General Directions’’. 


EXAMPLE 1. (HYDROQUINONE. ) 


(2).—The compound crystallizes in thin colorless needles melting in a capillary tube 
at 168°-169° (uncor.). It is odorless; tastes faintly bitter-sweet; and is soluble in ap- 
proximately 20 parts of cold water. (Time 28 minutes.) 

(3).—Ignited on platinum foil it leaves no ash. The tests after ignition with sodium in 
the iron tube show the absence of sulphur, nitrogen, and the halogens. It is therefore to be 
considered a species of Order I; and, because colorless, of Suborder I. (Time 20 minutes.) 

(4).—It does not give Generic Tests I or II. In the titration of Generic Test III, some 
alkali is consumed, but the final color transition is not sharp, and the slightly alkaline 
solution soon acquires a brownish color. The substance is therefore not’an acid, but may 
be a phenol. Test IV-1 gives a yellow-orange coloration. Test IV-2 gives a solution 
that rapidly turns brown on standing. The compound is hence a phenol. Turn to the 
analytical tables of Division A, Genus IV. (Time 22 minutes.) 

(5 and 6).—Of the ten phenolic species in the tables (p. 99) that melt between 163° 
and 173°, hydroquinone (m. p. 169°) appears to be the only one easily soluble in cold 
water. (The solubility given is 17 parts of water at 15°.) ‘The solubility in alcohol and 
ether, taste, YO coloration with ferric chloride in Test 401, power to reduce silver-nitrate 
solution on warming, and browning of the alkaline solution in the air, are found to be 
all properties of the substance which agree with those described for hydroquinone. The 
final confirmatory Test 411 (cf. p. 108) is next applied, and by oxidation with ferric-chloride 
solution, quinone is obtained. The quinone is recognized by its odor, and by conversion 
into quinhydrone, which forms green-black needles melting to a dark-red liquid at about 
170°, after previously beginning to soften at about 150°. (Time 40 minutes.) 

All the tests in the identification of hydroquinone were completed within 1 hour 
and 50 minutes, and 0.85 gram of hydroquinone was consumed. 


EXAMPLE 2, (MESITYLENE.) 


(2)—The compound is a colorless liquid which boils sharply between 163° and 163.5° 
(uncor.). Its specific gravity (determined in a capillary pyknometer (cf. p. 228) of known 
capacity, at 25°/4°) is 0.860. Its odor is aromatic; its taste slightly burning. It is in- 
soluble in cold water. (Time 30 minutes.) 

(3).—Ash constituents, sulphur, nitrogen, and the halogens are absent. The com- 
pound is to be sought among the species of Suborder I, Order 1. (Time 18 minutes.) 

(4) —Negative results are obtained in Generic Tests I, III, IV-1, VI, VII, and VIII, 
which are the only ones required for liquids. The compound must therefore be sought 
in Section 3 of Division B, Genus X (Liquid Hydrocarbons with Specific Gravity greater 
than 0.85 at 20°/4°). (Time 1 hour and 7 minutes.) 

Turning to the sections designated, it is found that of the six species mentioned with 
boiling-points between 159° and 169°, only two, p-methylethylbenzene, of B. P. 162°, 
mesitylene of B. P. 164.5° (cor.), and possibly tert. butylbenzene, B. P. 168°-8.5°, have 
specific gravities approximating that of the unknown compound. Specific Test 914 
(cf. p. 201) for mesitylene is therefore applied, and a white crystalline nitro derivative 
melting at 235° (uncor.) is obtained. The formation of this derivative, trinitromesitylene, 
proves the unknown substance to be mesitylene. (Time 60 minutes.) 

All the tests in this identification of mesitylene were completed in two hours and 
fifty-five minutes, with an expenditure of 0.87 gram of substance. 


CHAPTER II. 
ORDINAL TESTS. 


DIRECTIONS FOR THE DETECTION OF THE ELEMENTS IN AN ORGANIC COMPOUND. 





To determine the Order in which an unknown chemical species belongs usually 
involves a systematic qualitative examination for its component elements. This 
examination can be safely omitted only when the analyst’s knowledge of the origin 
of the compound is so complete that it is in itself demonstrative proof that certain 
elements must be, and alone can be, present. 

The qualitative procedure that will be given in this chapter makes provision 
for the detection of all the elements * that are of common occurrence in pure organic 
compounds, and will ensure the ready determination of the order of all species to 
be included in the ‘‘ Method”. Whenever a complete qualitative examination is 
called for, the several tests should be applied in the order in which they appear in the 
following lettered paragraphs: 


(a) Ignition Test for Carbon and Ash Constituents.—If reducible metals are 
probably absent, ignite a little of the substance on platinum foil; otherwise in a 
porcelain crucible. If the substance burns with a flame, or leaves a black carbon- 
aceous residue which gradually burns away, it may be considered organic. Care 
must, however, be taken not to mistake a permanent black residue consisting of 
a metallic oxide, like copper oxide, or of a reduced metal, like platinum, for carbon. 

If an incombustible ash is formed, incinerate a larger quantity of the substance 
in a crucible, and make a complete qualitative examination of the ash by the usual 
analytical methods. 

Should the ash contain a metallic element, it is probable that the original 
compound is a salt of some organic substance of acidic character. Since the 
‘“Method”’ only provides for the identification of metallic salts through the acids 
from which they are derived, it will be necessary, in dealing with a salt, to isolate 
its acid in a state of purity, preparatory to the location of the latter in the tables. 


(a’) Ignition Test for Carbon and Hydrogen.—It is rarely necessary to make any other 
test for carbon than that already given under (a); but the following more exact method 
is occasionally required: Place 0.1 gram of the substance mixed with five times its bulk 
of freshly ignited, dry, powdered copper oxide in an ignition-tube of hard glass, having an 
internal diameter of about 5 mm., anda length of 12 cm. Fill half the space remaining 
above the mixture with granulated copper oxide, and connect the open end of the tube 
with a bent gas-delivery tube leading into a narrow test-tube containing a few cubic 





* Oxygen and hydrogen form important exceptions to this general statement. A simple 
qualitative test for oxygen in combination, although much to be desired, is at present lacking. 
A test for hydrogen might always be applied, but the numerical preponderance of the hydrogen- 
containing species is so great—the present volume being without a single example of a coms 
pound in which this element is missing—that its general employment is unnecessary. % 


10 ORDINAL TESTS. 


centimeters of baryta solution. Support the ignition-tube in a horizontal position, and 
begin by heating that portion which contains the granulated copper oxide nearly to the 
temperature at which the glass begins to soften. This may be conveniently accomplished 
by use of a single Bunsen burner whose flame has been extended by a wing-top spreader. 
Next heat the mixture of substance and copper oxide by a second burner held in the hand, 
manipulating the flame so as to decompose the substance very gradually. The condensa- 
tion of drops of water on the glass at the cold end of the tube indicates the presence of 
hydrogen in the substance; the precipitation of barium carbonate in the test-tube, the 
presence of carbon. 

The above test, when applied to sulphur compounds, gives a precipitate of barium 
sulphate. In this case, allow the precipitate to settle without exposing to the air; decant 
the clear solution; cover the precipitate with a concentrated solution of potassium per- 
manganate; acidify with dilute sulphuric acid; and test the gas evolved for carbon dioxide. 
(The permanganate serves to oxidize the sulphur dioxide, thus preventing its escape when 
the solution is acidified.) 


SULPHUR, NITROGEN, PHOSPHORUS, CHLORINE, BROMINE, AND IODINE. 


Before applying the tests for these elements it is necessary to bring them 
into inorganic combination by fusing the organic substances containing them 
with metallic sodium. The analysis is then easily and quickly accomplished with 
an insignificant expenditure of material, even in the unusual case when all six 
elements are simultaneously present, and the product of the fusion consists of a 
mixture of alkaline sulphide, cyanide, (sulphocyanide), phosphide, chloride, 
bromide, and iodide. The manipulations connected with these tests, when once 
learned, will be found to offer no difficulties. The reliability of the process has 
been established by several years’ practical trial in the author’s laboratory. 

(b) Directions for the Ignition with Sodium.—Prepare an ignition-tube 8-10 
em. in length from a piece of hard-glass * combustion tubing. Support it in an 





* The employment of an iron or steel instead of a glass tube is usually permissible and 
preferable. Iig. 1 represents such a tube in use, suspended by the flange A through the per- 
forated asbestos-board screen B. The dimensions of 
these tubes should be: length, 9 cm.; internal diame- 
ter, 1.3 cm.; thickness of walls, 16 mm, They may 
now be obtained from the firm of Eimer & Amend of 
New York, by whom they are for sale under the name 
of ‘‘Tron Ignition-tubes for Use in Organic Analysis.” 
Unlike glass tubes they may be used for many successive 
fusions. After each experiment they should be allowed 
to stand filled with strong hydrochloric acid for several 
minutes, and then thoroughly cleaned by use of a test- 
tube brush and water. The manipulations in the test. 
are the same as with glass tubes, except that an iron 
tube may be rapidly cooled after the ignition by the 
application of cold water to its outer surface, as soon as. 
its temperature falls below visible redness. The time 
required to complete a test is thus materially shortened; 
and even when the tubes are iron castings, this practice, 
in the writer’s experience, has not» been the cause of any 
accidents. [As the opacity of the iron tube makes it. 
impossible to observe just when the free sodium is com- 
pletely destroyed after adding alcohol to it, the operator 
using this method should always be on his guard against 
the slight explosions that will follow a premature treat-. 
ment of the residue with water.] 

Since it is well known that nitrogen is fixed as cyanide. 

Fie. 1. when a mixture of sodium, iron powder, and carbona- 
ceous matter is strongly ignited with free access of air, it might be anticipated that iron would 














ORDINAL TESTS. 11 


exactly vertical position by a narrow metal clamp whose jaws are protected by 
being wrapped about by one or two layers of asbestos paper permanently wired on. 
Warm the closed end of the tube gradually before adding the sodium to lessen the 
danger of cracking the glass. Then drop in the sodium, which should be freshly 
cut from a large piece that has.been wiped free from all adhering oil by filter-paper. 
The sodium should weigh about a quarter of a gram, and will be of about the size 
of a pea. Place a burner flame directly underneath the tube and heat its lower 
end quickly to redness. As soon as the purple vapor of the melted metal is seen 
to form a layer more than a centimeter in depth, allow five drops of the substance 
if a liquid, or an equivalent quantity in fragments if a solid, to fall at intervals of 
one or two seconds directly upon the red-hot bottom of the tube without touching 
its side walls. The ensuing decomposition is almost instantaneous, and is some- 
times accompanied by slight but harmless explosions. The face of the operator 
should not be brought too close to the mouth of the tube during the reaction.* 

When the ignition-tube has become cold, remove the excess of sodium by 
adding 3 cc. of alcohol. Immediate addition of water is liable to cause explosions. 
As soon as the reaction between alcohol and sodium ceases, stir with a glass rod, 
and then pour cold water in cautiously, in small portions, until the tube is about 
two-thirds full. Finally stir again with a glass rod and rinse into a test-tube. Boil 
and filter. Dilute the alkaline filtrate, which will be nearly colorless if the fusion 
has been satisfactory, to about 20 ce. Separate portions of this filtrate, which 
will be designated as ‘‘S,’’ will be used in making the following tests: 

(c) Tests for Sulphur.—To | cc. of the alkaline ‘‘ solution 8”’, add two or three 
drops of a dilute sodium-nitroprusside solution. The presence of sulphur will be 
indicated by the immediate appearance of an intense, but not very permanent, 
purple coloration.—[It is best to prepare the reagent at the time when it is to be 
used, by dissolving a small crystal of nitroprusside in a little distilled water. 
Nitroprusside solutions do not keep well, though in the dry condition the sodium 
salt is very stable. ] 

As an alternative test for sulphur, prepare a clear alkaline solution containing 
lead, by mixing two or three drops of lead-acetate solution with several cubic 


prove an unsatisfactory substitute for glass in these ignition tests. But experiments have 
shown that even when the ignition is prolonged (unnecessarily) for five minutes after the 
addition of the last portion of the organic compound, only a scarcely perceptible blue stain is 
formed on the filter-paper in test (d) for nitrogen. ‘The tests for sulphur and halogens are 
not interfered with by the iron. The use of an iron tube is, however, not permissible when the 
test jor phosphorus is to be applied; for sodium appears always to take up some phosphorus 
or silicon when ignited in contact with cast iron. 

* The preliminary examination and the ignition test (a) will have given warning of danger 
if the substance under examination is a high explosive. Accidents from other compounds, if 
ordinary caution is observed, need not be feared. 

Liquids are best dropped into the tube from a medicine-dropper or small pipette. If the 
liquid is very volatile, its introduction will be much facilitated by passing the ignition-tube 
through a tight-fitting circular hole cut in the middle of a square screen of asbestos-board. This. 
screen, resting on the iron ring of a lamp-stand, shields the hand and dropper from the heat 
of the flame, and at the same time may be made to serve as a substitute for the clamp which 
would otherwise be used for holding the ignition-tube in position. The same screen may be 
used with tubes of smaller diameters if the tube 1s first fitted with a circular disc or washer cut 
from heavy asbestos paper. When in use, such a tube will be suspended from a point near the 
upper end by its washer, which will rest on the upper surface of the asbestos-board screen. By 
employing such screens, liquids whose boiling-points are very near the temperature of the labora- 
tory may be successfully treated. An improvement in the method for testing for nitrogen in 
small quantities of volatile or explosive substances in given in Vol. II, p. 3. 


12 ORDINAL TESTS. 


centimeters of a solution of sodium hydroxide [1:10], and add to 1 ce. of ‘‘S.” 
The presence of sulphur will be shown by the appearance of a black precipitate of 
lead sulphide. 

(d) Test for Nitrogen.—Boil 2 cc. of solution ‘‘S”’ for a minute or two with 
five drops of sodium-hydroxide solution and five drops of ferrous-sulphate solution. 
Then add just enough dilute hydrochloric acid to dissolve the precipitate of iron 
hydrates, and finally, a slight excess of ferric-chloride solution. A single drop 
of the last-named reagent will be enough, unless the solution should happen to 
contain much sodium sulphide, which would act on the ferric salt as a reducing 
agent. If no blue precipitate appears at once, allow the mixture to stand for a 
few minutes; then throw on a filter and wash with water. Presence of nitrogen 
will be indicated by a precipitate of Prussian blue. This precipitate, if scanty, 
may remain for some time in suspension, giving a turbid greenish appearance to 
the solution, which, in the absence of nitrogen, should merely show a pale yellow 
color due to the iron salts that have been added. After filtration, the Prussian 
blue in such a mixture will appear as a precipitate, or a very pronounced blue stain 
on the filter-paper. 

Test (d), so far as known, is universally applicable to all nitrogenous com- 
pounds except the diazo salts. These bodies when heated lose their nitrogen as 
a gas at such a low temperature that none of it reaches the sodium in a form that 
is convertible into cyanide. Diazo salts are, however, so well characterized by 
their physical and chemical properties, that they are not likely to be mistaken 
for species of the non-nitrogenous orders. 

(e) Test for Nitrogen and Sulphur when Present together.—Faintly acidify 
1 cc. of ‘‘S ” with hydrochloric acid, and add two or three drops of ferric-chloride 
solution. A red coloration (ferric sulphocyanide) indicates the presence of sul- 
phur and nitrogen. This test may be omitted when (c) and (d) have both given a 
positive result. 

When a sufficient excess of sodium is used * for the fusion, no sulphocyanide 
will ever be met with at this point, as, at the temperature of the fusion, sulpho- 
cyanides are decomposed by the alkali metal to form sulphide and cyanide. It 
therefore rarely happens that sulphur and nitrogen are not detected by tests (c) 
and (d). 

(f) Test for Phosphorus.—Boil 1 cc. of solution ‘‘S” with 3 ec. of concen- 
trated nitric acid. Cool; mix with two volumes of the ordinary acid ammonium- 
molybdate reagent; warm to 50°; and allow to stand for ten or fifteen minutes. 
A pulverulent yellow precipitate indicates phosphorus—(in the absence of arsenic). 

A portion of the phosphorus originally combined as sodium phosphide is lost 
as phosphoretted hydrogen when the solution ‘‘S” 1s prepared from the fused 
mass. Enough, however, remains to give a satisfactory phosphomolybdate pre- 
cipitate in test (f). 

(g) Tests for Halogens.—Two cases are to be distinguished :— 

(1) When sulphur and nitrogen are both absent, acidify 1 cc. of solution ‘‘S ” 
with nitric acid and add silver nitrate. If a precipitate of silver halide appears, 





* Cf. Tauber, Ber. 32, 3150. 


ORDINAL TESTS. 13 


place the remainder of ‘‘S ” in a very small porcelain dish; add dilute sulphuric 
acid to faint acid reaction; and boil down to one third of the initial volume. The 
boiling is to remove alcohol, which may interfere with test (i), in which chromic 
acid is employed. Dilute the concentrated solution to 20 cc. Under the name 
of solution ‘‘ H”’ it will be used for tests (h), (i), and (j). 

(2) If evther sulphur or nitrogen has been found, prepare solution “ H’’ first, 
and use 1 cc. of it instead of “S” in making test (1) with silver nitrate. In the 
preparation of “H” the sulphur will usually have been completely expelled as 
hydrogen sulphide, and the nitrogen as hydrocyanic acid, so that if no precipitate 
is obtained, it will be safe to conclude that the halogens are all absent. : 

To detect several halogens in presence of one another, the following analytical 
scheme, based on the principles used in Carnot’s method for their quantitative 
separation, is recommended as direct and reliable. The complications and mistakes 
which are liable to occur in using other procedures when a solution contains sulpho- 
cyanide, or when all hydrocyanic acid and sulphuretted hydrogen have not been 
removed in the preparation of ‘‘ solution H,” are here rendered impossible in conse- 
quence of the complete oxidation or expulsion of the disturbing compounds that 
occurs during the operations in the test for bromine in (i). 


(h) Test for Iodine.—Place ‘solution H”’ in a 50-cc. separatory funnel, add 
3 drops of the nitrosyl-sulphate solution whose preparation is described in the foot- 
note,* and shake out thoroughly with 5 cc. of carbon disulphide. If iodine is present 
it will be liberated and taken up by the disulphide, which will acquire an amethys- 
tine purple color. Shake out with fresh portions of the disulphide until the last 
portion added is removed colorless. Then add two or three more drops of the 
nitrosyl-sulphate solution, and repeat the operations described until it is certain 
that all the iodine has been removed. 


(i) Test for Bromine.—After the separation of iodine by the method described 
in the last paragraph, filter the solution through a wet filter to remove the last of 
the carbon disulphide and transfer to a 75- or 100-cc. round-bottomed flask. 
Support the latter in a slightly inclined position by means of a clamp, and add to 
its contents 0.7 grm. of powdered potassium dichromate (free from chloride) 
and 6 cc. of dilute sulphuric acid. Rinse out the neck of the flask with a little 
distilled water. Drop in an ebullator tube (cf. p. 223), and then boil the solution 
briskly over a free flame. Just before boiling begins, insert a short roll of fluorescein 





* Nitrosyl-sulphuric Acid Solution —Grind together in a mortar 15 grms. of starch and an 
equal weight of water. Pour the thick cream into a 300-ce. distilling-flask, heated by a boiling 
water-bath, and then add to it 30 cc. of pure nitric acid (sp, gr. 1.35). The flask is to be pro- 
vided with a dropping-funnel, and with a delivery-tube for conveying the oxides of nitrogen 
that will be evolved, into 30 cc. of concentrated sulphuric acid, in which they are to be absorbed. 
The sulphuric acid should be placed in a small flask surrounded by cold water. A small empty 
bottle should be interposed between the distilling-flask and the sulphuric acid to condense 
most of the water and nitric acid that pass over with the gases. Heat the mixture in the flask 
until a vigorous evolution of gas sets in. When this begins to slacken, gradually admit into 
the flask through the dropping-funnel 60 cc. more of the nitric acid of 1.35 specific gravity, 
and continue the heating as long as the oxides of nitrogen are given off freely. The product is 
a nearly saturated solution of nitrosyl-sulphuric acid in sulphuric acid. In a closed bottle it _ 


keeps indefinitely. 
2H.SO,+N,0; =H,0 + 2NO.0.S0,.0H. 


14 ORDINAL TESTS. 


paper * for half its length into the mouth of the flask. If the solution contains 
bromide, bromine vapors will be liberated. These vapors mixed with the hot steam 
change the lemon-yellow color of the test-paper to a rose-pink. Chlorine is not set 
free. The test with fluorescein must be repeated at intervals of two minutes, 
using fresh portions of the test-paper each time, until it is certain that the last trace 
of bromine has been expelled. 

(j) Test for Chlorine.—Dilute “H,” after the removal of iodine and bromine, 
to at least 50 cc.; add 2 or 3 cc. of dilute nitric acid; bring to a boil and test for 
chlorine with silver nitrate. If a precipitate which remains reddish after washing is 
formed, it is probably colored by silver chromate. In such a case it should be 
redissolved in a little warm ammonia, and after dilution reprecipitated by nitric 
acid. The precipitate, if silver chloride, will now be white. 


DETERMINATION OF THE SUBORDER. 


The colorless species of every order form its first suborder, and its colored 
species its second suborder. ‘The position in the classification of compounds that 
are only very slightly colored is fixed by rules stated on page 204. 


* Fluorescein Paper.—This is prepared by soaking filter-paper in a filtered solution con- 
taining one part of fluorescein in two hundred parts of 50 per cent acetic acid. The paper, 
which should then have a clear lemon-yellow color, is quickly air-dried, cut in strips, and pre- 
served in stoppered bottles. It keeps well when not exposed to bright sunlight. The change 
in color produced in this paper in test (i) by the mixture of bromine vapor and dry steam is 
due to the formation of eosine (tetrabromfluorescein). 


CHAPTER IIL 
Gi NiUisy I MEDI el a ADI sks) 


OF 
SUBORDER I, ORDER I. 


(Colorless Compounds of Carbon, Hydrogen, and Oxygen.) 


This genus is by definition made to include all species of the suborder which give . 
Generic Test I. The definition admits to the group in addition to the true aldehydes 
those acetals that are partially hydrolyzed to aldehydes under the conditions of the test, but 
excludes the aldose carbohydrates. 


GENERIC TEST I. 


ADD 0.05 GRM. OF THE FINELY POWDERED SUBSTANCE, IF IT IS A SOLID, OR ONE 
DROP, IF IT IS A LIQUID, TO 5 CC. OF A FUCHSINE ALDEHYDE REAGENT * 
THAT HAS BEEN PREPARED BY THE METHOD DESCRIBED BELOW. IF THE 
SUBSTANCE DISSOLVES, ALLOW THE SOLUTION TO STAND TWO MINUTES 
AND THEN OBSERVE THE COLOR. IF THE SUBSTANCE DOES NOT DISSOLVE, 
SHAKE THE TEST-TUBE CONTAINING IT GENTLY FOR TWO MINUTES AND 
THEN OBSERVE THE COLOR. NEVER APPLY HEAT. 

THE APPEARANCE OF A DISTINCT PINK, RED, PURPLE, OR BLUE COLORATION IN 
THE SOLUTION WITHIN THE TIME LIMIT INDICATES THAT THE COMPOUND 
TESTED SHOULD BE SOUGHT FOR IN THE TABLES OF THIS GENUS. IF THE 
SUBSTANCE IS A SOLID, AND NO COLORATION IS OBTAINED, PASS ON TO GEN- 
ERIC TEST II; IF A LIQUID, TO GENERIC TEST III. 

Observations on Generic Test I. 

Soluble aldehydes usually color the fuchsine reagent within a few seconds; 
those which are difficultly soluble and of high molecular weight sometimes require 
the full two minutes. Solid substances which for any reason are suspected to 
be polymerized aldehydes should be boiled with 5 cc. of water containing a 
drop of strong hydrochloric acid, if no color appears within the time limit, 
and a few drops of the cooled solution then added to the reagent. Enough of 
the compound (e.g. metaldehyde) may thus be depolymerized to give a good 
reaction. 

Ordinary acetone and some other soluble ketones prepared by destructive 


distillation gradually redden the reagent if added to it in large quantity, or allowed 








* (The Fuchsine Aldehyde Reagent.—Dissolve 0.2 grm. of rosaniline, or, if the free base 
can not be obtained, of the hydrochloride or acetate, in 10 cc. of a freshly prepared, cold, saturated 
aqueous solution of sulphur dioxide. Allow the solution to stand until all signs of pink dis- 
appear and it becomes colorless or pale yellow. This will require several hours. ‘Then dilute 
with water to 200 cc. and preserve for use in a tightly stoppered bottle. 

This reagent keeps well if not unnecessarily exposed to air and light, and should always 
be kept on hand. The directions for its preparation should be followed with care, since any 
large increase of sulphurous acid above the quantity specified diminishes its sensitiveness so 
much as to render it unserviceable in testing for the less reactive aromatic aldehydes like sali- 
cylic aldehyde, vanilline, etc. A reagent that has been in use many months and is found to 
have lost sensitiveness may be re-sensitized by the cautious addition of sodium acetate, stop- 
ping at the moment when a faint pink coloration begins to appear, and then discharging this 
color by a few drops of the oxidized solution held in reserve for the purpose. In this connec- 
tion it should be stated, by way of caution, that free alkali, or the alkali salts of any weak acid, 
organic or inorganic, will redden the reagent like an aldehyde. It is also reddened by heat or 
when exposed in small quantities to the air for some hours at the ordinary temperature. Min- 
eral acids greatly diminish its sensitiveness. | 

15 


16 CHARACTERISTICS OF THE ALDEHYDES. 


to remain in contact with it for a number of minutes; but the color is due chiefly, if 
not wholly, to the presence of traces of aldehydes or acetals. The limits set upon 
the quantity of material used, and the time allowed for the development of a distinct 
coloration, are, therefore, both conditions that must not be disregarded. The 
reaction is so delicate that the traces of aldehydes occurring as impurities in many 
commercial preparations may make trouble if their preliminary purification is 
neglected. But if the conditions prescribed for the test are carefully observed, the 
best commercial preparations of bodies belonging to other genera rarely give any 
color within two minutes.* 


General Physical and Chemical Characteristics of the Aldehydes. 

Nearly all aldehydes of the liquid division are distinguished by characteristic odors, 
which, for the more volatile species, may be described as ethereal and at the same time irri- 
tating or pungent; and for the higher boiling ones, as aromatic, fragrant, or spicy. The 
solid aldehydes are either odorless or have odors similar to those of the higher boiling 
liquid aldehydes, though as a rule less intense. 

Genus I is notable chemically for the great reactivity of its species. Brief contact 
with small quantities of concentrated mineral acids, aikalies, or certain metallic salts 
often causes gradual or sudden polymerization of aldehydes to more stable “para” or “meta” 
modifications, which would entirely fail to give aldehydic reactions were it not for their 
tendency to dissociate to some slight extent, under the influence of reagents, to the parent 
compounds. 

Since the liquid aldehydes are gradually oxidized to acids by exposure to the air, 
commercial preparations of the species of Division 2 will often be found to react acid towards 
litmus or phenolphthalein. Aldehydes are readily oxidized by alkaline permanganate 
in Test 304, and by ammoniacal silver nitrate in Test 101. The latter reaction, which 
is accompanied by the formation of a silver mirror, or a precipitate of finely divided metallic 
silver, is a simple and valuable test. 

Aldehydes usually dissolve in concentrated sulphuric acid with decomposition. Hot 
solutions of caustic alkali attack them with greater or less ease, according to the species, 
forming salts of organic acids that are sometimes accompanied by other products. Bro- 
uiine reacts with them readily, hydrobromic acid being evolved. Metallic sodium attacks 
them much as it does alcohols or phenols, hydrogen being sometimes liberated. Phenylhy- 
drazine, hydroxylamine, and aniline condense with them to hydrazones, oximes, and anils, 
compounds which often crystallize well and are very valuable in the identification of in- 
dividual species. Phenylhydrazine, applied in the manner directed in generic Test VII-2 
for ketones, is also a very sensitive general reagent for the detection of the carbonyl radical 
in aldehydes; but many species in the genera intervening between I and VII likewise 
react with it. 

Towards certain reagents like sodium bisulphite, many aldehydes, as well as ketones, 
act like unsaturated compounds. A concentrated bisulphite solution, when vigorously 
shaken in a test-tube with an equal volume of a liquid aldehyde, or with a concentrated 
ethereal solution of a solid aldehyde, frequently evolves heat and solidifies, either at 
once, or after being cooled and shaken, to a thick crystalline magma of the composition 
R.C.H(OH)(SO,Na), from which the original aldehyde may be recovered by treatment 
with an alkali or an acid. A negative result from this test does not prove that a sub- 
stance is not an aldehyde, for many bisulphite addition-products are too soluble in 
water to appear as precipitates, while others do not combine readily with the reagent. 
Many ketones, moreover, show the same behavior with the reagent as aldehydes. 











* Thus, among the alcohols prepared by Kahlbaum, benzyl and allyl alcohols were the only 
ores which were found to be sufhciently contaminated with an aldehyde to give this test. 


COLORLESS COMPOUNDS CONTAINING C, H, AND 0 [SUBORDER I OF ORDER II. 


GENUS I, ALDEHYDES. 


DIVISION A,—SOLID ALDEHYDES. 





Melting-point 
(C.°). 





35 
37 


37 


40 


44-5 
45-6 


51 
‘52 
52-5 
52-53 
5A 
56 
58-5 
59-60 
61 


63-5 
80-81 


ALDEHYDES.—Colorless and Solid. 





o-Methoxybenzoic Ald., MeO.C,H,.CHO.—After fusion remelts at 3°.—I. aq.; 
e. S.eth.;s. alc. B. p. 248°-4° C. 

Acetylsalicylic Ald., o-C,H,0.0.C,H,.CHO.—B. p. 253° (sl. dec.). Cryst. mass 
v. s. alc, or eth. 

{ Piperonal (Heliotropine), CH,.0,.C,H,.CHO.—B. p. 263°. Odor of helio- 
trope! Ndl. fr. h. aq.; s. 500-600 pts. c. aq.; e. s. ale. or eth.—}t Warm 
0.1 grm. gently with nitric acid (sp. gr. 1-40); precipitate nitro comp. 
with cold water; cryst. fr. h. aq.; m. p. of dry, pale-yellow silky ndl. 95-5°. 

Propionylpropionic Ald.,Et. CO.CHMe.CHO.—B. p. 164-6°. Tbl. s. aq.; v. 
s.alec. Alc. sol. dark violet w. FeCl. 

Lauric Ald., C,,H,;.CHO.—Cryst. mass. 

t Metacrolein, (C,H,O),.—Cryst.; odor spicy.—Distill. Pass irritating acro- 
lein vapors liberated into 2 cc. aq., and apply Test 112. 

Furfuracrolein, C,H,O.CHO.—B. p. a. 200° w. dec.—Cinnamon odor.—D. s, 
aq.; e. s. ale. or eth.; s. glacial Ac. containing aniline w. green color! 

I, 2, 3-Irimethylbenzoic Ald., Me,.C,H,.CHO.—Nadl. fr. dil. alc. 

Myristic Ald., C,,H,;.CHO.—B. p. 168°-169° (22 mm.). 

Polycenanthylic Ald., (C,;H,,0)z.—I. aq.; v.s. alc. oreth. Dist. gives cenan- 
thylic aldehyde. 

o-Oxy-p-toluic Ald., Me.C,H,(OH)CHO.—B. p. 222°-3°.—Violet w. FeCl;.— 
Sol. in ammonia w. deep-yellow color. 

o-Oxy-m-toluic Ald., Me.C,H,(OH)CHO.—B. p. 217°-8°.—Deep-blue color w. 
FeCl,.—Ammon. sol. deep yellow, 

+ Palmitic Ald:, C,,H;,.CHO.—B. p. 192°-3° (22 mm.). Pearly scales d. s. ¢. 
eth. 

Paraisobutyric Ald., (C,H,O),.—B. p. 195°C. Ndl. fr. aq. or alc. Heated w. 
H,SO, gives isobutyric aldehyde. 

8-Naphthoic Ald., C,,H,.CHO.—Lits. fr. h. aq.; v. s. alc. or eth. 

Stearic Ald., C,,H,,-CHO.—B. p. 212°-3° (22 mm.). Scales fr. eth. 

+ Vanilline, C,H,.(Me0)(OH)(CHO)(3 : 4: 1).—Slender ndl. fr. h. aq.; s. in 
20 pt. h. aq. or in 90-100 pt. c. aq; e. s. alc., eth., or CHCl, Strong 
vanilla odor! Taste at first burning, then like vanilla! Aq. sol. (1 : 200) 
gives immediate blue coloration w FeCl, in Test 401.—Dissolve 0.05 grm. 
in 10 cc. aq. Add 2 drops conc. HCl and 2 drops FeCl, sol. (1:10). Boil 
one minute. Filter hot. Wash. Boil residue w. 5 cc strong alcohol. 
Filter; dry at 100° and determine melting-point The product, dehy- 
drodivanilline, forms slender, nearly colorless, silky microcrystalline ndl. 
melting w. dec, at abt 304° (uncor.). 

o-Aldehydobenzoic Ac., CO,H.C,H,.CHO.—Lits. v.s. aq., ale. oreth. Ag salt 
ervst. in ndl. fr. h. aq —NH, gas passed into alc. sol. gives cryst. comp. 
m. p. 187°. [Gives Test I w. the fuchsine reagent, (A. 239, 82) ] 

m-Oxybenzoic Ald., HO.C,H,.CHO.—B. p. 240° Ndi. fr. h. aq.—Sol. violet 
w. FeCl,; gives ppt. w. Pb.Ac,. Heating w. X’s acetic anhydride gives 
diacetate, m. p. 76°. 

Trimethyl-o-oxybenzoic Ald., Me,.C,H(OH).CHO.—Pale-yellow ndl.; i. aq. 
or KOH; s. ale. or eth. Sublimes. 


nen nnn ae 
17 


18 


Melting-point 
(C.°). 
110 


Sbl. 112-15 


115 
115-16 
Sbl. abt. 120 
128 


130 
164-6 


175 


179 


180 
221-2 


234 
237-8d. 
243-4 


247 
248-9 


260d. 


285 


GENUS I, DIV. A, 


(ORDER I, SUBORDER I.) 





ALDEHYDES.—Colorless and Solid. 








p-Oxy-o-toluic Ald., Me.C,H,OH.CHO.—ThbIl.s. h. aq.; e.s. ale.,oreth. Rose 


red w. FeC],. Ammonia sol. colorless. 

+ Metaldehyde, (C,H,O,)7.— I. aq.; d.s. eth., ale. Dist. w. dil. H,SO, gives 
acetaldehyde (Test 111). For behavior toward reagents cf. remark on 
page 15. : 

p-Oxy-m-toluic Ald., Me.C,H,(OH)CHO.—Pr. fr. aq.—Blue-violet color w. 
FeCl;. . 

p-Oxybenzoic Ald., HO.C,H,.CHO.—Sbl. undec. D.s. c. aq.; e. s. ale., eth, 
Pale-violet color w. FeCl,.—For derivative cf. Paal, Ber. 28, 2409. 

+ Paraformaldehyde (commercial), (CH,O)z.—Odor and reactions like form- 
aldehyde. White amorphous powder.—Apply Test 114-1. 

Disalicylic Ald., C,,H,,O;—Sbl. undec. Almost i. aq. or KOH; e.s. alc., eth. 
Cold conc. H,SO, gives salicylic ald. 

Dialdane, C,H,,0;.—Cryst. v. d. s. aq., eth.; e. 8. h. alec. 

m-Aldehydobenzoic Ac., CO,H.C,H,.CHO.—Cu salt green-blue ndl. 
Weel Go. ee 

Helicine, C,,H,,0;—(Cryst. w. }H,O, which is lost at 100°.) Small ndl. s. 
64 pt. aq. at 8°: i. eth_—No color w. FeCl;. Dil. min. acids hydrolyze to 
dextrose and salicylic aldehyde. Opt. act. 

(v-)m-Aldehydosalicylic Ac., (HO)(CO,I1).C,H,.CHO.—Sbl. 
yellow color in NaOH—Sol. red w. FeCl. 

Metapropionic Ald., (C;H,O)z.—‘Sbl. fr. 160°. I. aq.; v.d.s. ale. 

Aldehydovanillic Ac., MeO.C,H,.(OH)(CO,H)(CHO).—Silky ndl. v. d. s. ¢. aq.; 
s. eth.—Yellow sol. in NaOH. Dingy-violet color w. FeCl. 

p-Aldehydo-m-oxybenzoic Ac., CHO.C,H,(OH)CO,H.—Ndl. d.s. h. aq.; e.s, 
ale. or eth.—Sol. in NaOH is deep vellow.—Gives violet color w. FeCl,. 

Aldehydo-(v)-oxyisophthalic Ac., CHO.C,H,.(OH)(CO,H),.—S, h. aq.; e. s, 
eth.—Sol. cherry-red w. FeCl,;.NaOH sol. colorless! 

m-Aldehydo-p-oxybenzoic Ac., CHO.C,H,(OH)CO,H.—D.s.aq.; e.s.eth. Aq. 
sol. brick-red w. FeCl,. NaOH sol. deep yellow! 

p-Aldehydocinnamic Ac., CHO.C,H,.C,H,.CO,H.—Sbl. in Ifts. D. s, eth. 

(a-)m-Aldehydosalicylic Ac., CHO.C,H;(OH)CO,H.—D. s. h. aq.; e. s. eth. 
‘NaOH sol. colorless. FeCl, gives red color to aq. sol. 

Aldehydo-(a)-oxyisophthalic Ac., CHO.C,H,OH.(CO,H),.—Nd1. fr. h. aq., e. s. 
eth. Does not sublime. Blood-red color w. FeCl,. Alkali solutions are 
yellow w. green fluorescence. 

p-Aldehydobenzoic Ac., CHO.C,H,.CO,H.—Sbl. in small ndl. 
aq.—Ndl. fr. aq. 


Oxime 


5. baa we 


D. s. ath or h, 





COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I}. 


Boiling-point 
WON 


20-8 
45-5 


48 -8c. 


GENUS I, ALDEHYDES. 


DIVISION B,—LIQUID ALDEHYDES. 


ALDEHYDES.—Colorless and Liquid. 


t Acetic Ald.. Me.CHO.—G. 0-8056°/,. Odor pungent-ethereal, stifling! 


Misc. w. aq., alc., or eth_— Apply Test 111! 

{ Methylal, CH,.(OMe),.—G. 0-8721°/,. Odor alcoholic.—E. s. aq.— Apply 
formic aldehyde Test 114-1 to dil. aq. sol. 

t Propionic Ald., Et.CHO.—G. 0-80667°/,. S.in 5 pts. aq. at 20°. Odor pun- 
gent.—Warm w. 2 pts. phenylhydrazine; wash hydrazone w. dil. acetic 
acid; then heat w. an equal wt. ZnCl, at 180°. Disgusting skatol odor is 
produced. 

t Acrolein, CH, :CH.CHO.—G. 0-84. Vapor excessively irritating; in traces 
provokes flow of tears. EE. s. aq.—Polymerizes to i. solid so readily that 
it can not long be preserved liquid.—Apply Test 112! 

Propargyl Ald., CH:C.CHO.—E. s. aq. Very irritating to mucous mem- 
branes. Gives orange ppt. with ammon. Cu,Cl, sol! 

{ Isobutyric Ald., C,H,.CHO.—G. 0-79387°/,. S.in9 vol aq.—NaHSO, comp. 
pearly Ifts. rather d. s. aq. 

Dimethylacetal, Me.CH.(OMe),.—G. 0-866 at 22°. 

n-Butyric Ald., Pr.CHO.—G. 0-8170°/,. S. in 27 pt. aq.—NaHSO, comp. e. 
s. aq. or alc. 

Trimethylacetic Ald., Me,.C.CHO.—G. 0-7927 (18°). 

Methylene-diethyl Ether, CH,.(OEt),.—G. 0-851 (0°). S. in 11 vol. aq.— Not 
acted on by h. KOH. 

+ Isovalerianic Ald., C,H,.CHO.—G. 0-82 (0°). Odor when free fr. valerianic 
ac. sweet and aromatic. Shaken w. conc. ammonia solidifies to cryst. 
comp. (m. p. 56°-8°). 

+ Formic Ald., (commercial ‘‘40 per cent solution” in water). Distillation 
leaves white residue of ‘‘ paraformaldehyde” in flask. Odor pungent. 
Apply Test 114! 

n-Valerianic Ald., C,H,.CHO.—G. 0-82 (11.2°). 

+ Acetal, Me.CH.(OEt),.—G. 0-8314”°/,. Odor agreeable and refreshing—not 
irritating.—S. in 18 vol. ec. aq. The dil. aq. sol. if first mixed with a few 
drops of HCl gives acetaldehyde (Test 111). (Boiling with NaOH gives 
no acetaldehyde.) 

a-Crotonic Ald., Me.CH:CH.CHO.—G. 1-033°/,. Odor fruity, then irritat- 
ing. Absorbs O, and adds Br, easily. 

Tetramethylene Ald., C,H,.CHO. 

Tiglic Ald., Me.CH:CMe.CHO.—G 0-87 (15°). Odor like bitter almonds. 
S. in 40-50 pt. aq. Air oxid. easily. 

Isobutylacetic Ald., C,H,.CH,.CHO.—Odor aromatic. 

+ Paraldehyde, (C,H,O),.—G. 0-9992 at 15°. M. p. 10°.5. Odor ethereal, 
agreeable. S. in 10 pt. aq. Heated with a very little conc. H,SO, 
gives off acetic aldehyde freely. Pure, does not give acetic aldehyde 
(Test 111) distinctly. Solidified by freezing mixture. M. p. +-12.5° 

n-Caproic Ald., C;H,,.CHO.—G. 0-8498 at 0°. 

Methylethylacrolein, Et.CH:CMe.CHO.—G. 0-8577 at 20°. Almost i. aq, 
Odor penetrating. 





en nt EID EL ne ee 


19 


20 


Boiling-point 
(C2). 





146:8 


155 
160-2 


161 


161 -2d. 
166- 2c. 


169-6 
169-70 


170-1d. 


179-5 


186-8d. 


186-8 


187 (th. i.) 


188-92 
193-4 


196-5e 


199 


200 
204 


205-8 
208 
208-9 
210-8c. 
228-9 
230 
230 


235 


235—40 


GENUS I, DIV. B. 


(ORDER I, SUBORDER I.) 


ALDEHYDES.—Colorless and Liquid. 


Ethylidenedipropyl Ether, CH,.CH.(OPr),.—G. 0-825 at 22°. I. aq.; s. cone. 
Cl 


1. Reduces ammon. AgNO; sol.—Not attacked by hot KOH. 

{ G@nanthic Ald., C,H,,.CHO.—G. 0-84957°/,. Odor aromatic. 

Ethyl Methylformylacetate, CO,Et.CH.Me.CHO.—Gives intense red-violet 
coloration w. FeCl. 

} Furfurol, C,H,0.CHO.—G. 1-1594”/,. Darkens on exposure to light. Odor 
remotely ‘resembles that of bitter almonds and cinnamon. —Apply Test 
15. 

[Glycid, cf. Genus VIII.} Dist. w. dee. giving acrolein (Test 112). 

Propylidinedipropyl Ether, Et.CH.(OPr);.—G. 0-8495 at 0°. 

Isocapric Ald., C)H,,.CHO.—G. 0-828 at 0°. NaHSO, gives no comp. 

Parapropionic Ald., (C,H,O),.—I. aq. _ Dist. w. a drop or two of cone. H,SO, 
gives much propionic ald. 

4‘, °-Dihydrobenzaldehyde, C,H,O.—G. 1-0327 at 0°. Oil w. penetrating 
odor. 

+ Benzaldehyde, Ph.CHO.—G. 1-0504."°/,.. Bitter-almond odor. S. in abt. 
300 pt. aq.—Apply Test 113. 

Levulinic Ald., Me.CO.(CH,),.CHO.—G. 1-0156 at 16°. ‘‘Odor aldehydic.” 
Misc. w. aq. —Reduces Fehling’s sol. in the cold. Colored red by cone. 
FES) 

Tetrahydrobenzaldehyde, C,H,,O.—G. 1-0091 at.0°. J. aq. Odor like ace- 
tone and bitter almonds. Reduces Fehling’s sol. in cold. 

Methylfurfurol, Me.C,H,O.CHO.—G., 1-1087 at 18°. 5. in 30 pt. aq.—1 drop 
in 5 ce. ale. +1 ce. conc. sulphuric acid gives green color. Conc. ammonia 
gives the furfuramide (m. p. 86—7°, ndl. fr. dil. alc.). : 

Diisovalerianic Ald., C,)H,,0.—G. 0-861 at 0°.. I. aq.; \e. s. ale. Odor 
aromatic. 

Phenylacetic Ald., Ph.CH,.CHO.—G. 1-085. Phenylhydrazone ndl. irgr 
m. p: 537. 

t Salicylic Ald., o-HO.C,H,.CHO.—G. 1-173 at13°. Odorfaint aromatic. D. 
S. 2057 Vass ale. or eth, Aq. sol. gives w. FeCl, intense violet color was 
vert into the phenylhydrazone. / 

m-Toluic Ald., Me.C,H,.CHO.—G. 1-037 at 0°. Bitter-almond sad Pre- 
pare corresponding phenylhydrazone, m, p. abt. 90°. 
o-Toluic Ald., Me.C,H,.CHO.—M. p. of oxime 48°—49°, 

p-Toluic Ald., Me.C,H,.CHO.—Odor pepper-like.—M. p. of oximes 79°-80°, 
and 108°-110°. 

} Citronellal, C,H,,.CHO.—G. 0-8538 at 17.5°. Strong geranium-like odor! 
Opt. active. Identify by conversion into its semicarbazide of mp. 84°. 
(Cf. Ber. 31, 3307.) 

Hydrocinnamic Ald., Ph.C,H,.CHO. 

(v)-o-Oxy-m-toluic Ald., Me.C,H,OH.CHO.—M. p.17°. D.s. aq.; e. 8. eth._— 
Sol in ammonia yellow. Sol. in FeCl, bluish. . 

Ethylidene-diisoamyl Ether, Me.CH.(OC,H,,),.—G. 0-8347 at 15°. 

{ Citral, C,H, ,.CHO.—G. 0-8972 at 15°. Odor of oil of lemon! Opt. active, 
—Identify by converting into the semicarbazide of m. p. 164° (cf. Ber. 
31, 3331). 

m-Oxybenzoicaldehydemethylether, MeO.C,H,.CHO.—G. 1-11877°/,. Formsa_ 
d.s. NaHSO, comp. ; 

£-Diisobutylene Ald., C,H,,0.—G. 0-9575 at 0°. Thick oil of agreeable odor. 
Resinified by h. NaOH sol. 

{ Cuminic Ald., p-Me,.CH.C,H,.CHO.—G. 0-9832 at 0°. Odor aromatic and 
characteristic. Gives terephthalic ac.( cf. Test 318).—Color reaction with 
H,SO0, (A. 137, 104).. + Phenylhydrazone deriv. white but unstable (m. p. 
127° 139°), 

I, 3, 5-Lrimethylbenzoic Ald., Me,.C ‘A, -CHO. | 





GENUS I, DIV. B. 21 


(ORDER I, SUBORDER I.) 











a hae ALDEHYDES.—Colorless and Liquid. 
245 m-Oxybenzoicaldehyde-ethylether, EtO.C,H,.CHO.—G. 1-07687°/,. Yellow oil. 
248c. + Anisic Ald., p-MeO.C,H,.CHO.—G. 1-1228 at 18°. M. p. 0°. Odor aro- 


matic. Hot ale. KOH gives anisic ac. and anisic alecohol.—f Prepare the 
phenylhydrazone, a pearly-white ppt., m. p. 120° (uncor.). Procedure 
exactly as in Test 113-1, except that only half the quantity of dilute 
alcohol there prescribed should be used in each operation. 


279 Dicenanthylic Ald., C,,H,,0.—G. 0-8494 at 15°. Oil with faint odor. 





[Important aldehydes that can be distilled only under reduced pressure. ] 


128-30 (20 mm.)| { Cinnamic Ald., Ph.C,H,.CHO.—G. 1-0497%*/,. Odor like cinnamon, © 
- changed by shaking w. excess of permanganate sol. [1 : 10] to odor of 
benzaldehyde.—t Prepare the phenylhvdrazone by method given in 
Test 113-1, except that the product should be boiled up three times with 
15 ce. of 50 per cent alcohol, instead of twice with 12cc. This hydrazone 
is yellow (YT1-YT2), and melts at 168° (uncor.). 


SS SS SS 


NUMBERED SPECIFIC AND SEMI-SPECIFIC ALDEHYDE 
TESTS. 


[TESTS 101-200.] 


101. Compounds Reducing Silver from Tollen’s Reagent. 


Place 1-2 drops, or about 0.05 grm., of the finely powdered substance in a test-tube 
with 2-3 cc. of the reagent (whose preparation is described below *). Shake and allow 
to stand without warming for about five minutes. 

A black or brownish-black precipitate of metallic silver, or a silver mirror adhering 
to the walls of the tube, shows that the compound has silver-reducing power and may be an 
aldehyde. Outside of Order I, Genus I, many scattered species reduce silver from Tollen’s 
reagent. Representative bodies of this description are glucose among the carbohydrates, 
and hydroquinone among the polyacidic phenols. So far as it is known, this reaction 
fails among the aldehydes only in the case of a few aromatic oxy-aldehydes like salicylic 
aldehyde and vanilline. It is generally a very delicate and satisfactory reaction. 


111. Acetaldehyde. (Properties tabulated on p. 19.) 


1. Boil 1 ce. of a clear aqueous solution of the aldehyde that is concentrated enough 
to have a distinctly pungent odor with 5 cc. of sodium hydroxide solution (1:10) for a 
minute or two. The solution, which at first assumes a clear-yellow color, soon becomes 
turbid, opaque, and yellow orange (YOSI) from separation of finely divided acetaldehyde 
resin. At the same time a peculiar, penetrating and rather persistent odor is given off. 
Although many other aldehydes give colorations to boiling soda solution, and emit odors 
during treatment, this reaction when applied comparatively, or when the odor and color 
are both familiar from earlier experience, is a delicate and characteristic preliminary test. 

Propionic aldehyde, which resembles acetaldehyde more closely in its physical proper- 
ties than any other species in its genus, gives a somewhat similar odor and turbidity; but 
the turbidity is less conspicuous in dilute solutions, is nearly white instead of yellow- 
orange and entirely disappears if the boiling is long continued. Half a drop of acet- 
aldehyde, for instance, when boiled with 5 cc. of the soda solution is enough to give the 
test as described; while three drops of propionic aldehyde under the same circumstances 
give only a milky-white precipitate which disappears on continued boiling with emission 
of astrong lemon-like odor. The lemon odor is usually noticeable in testing acetaldehyde, 
but is not the dominant odor. | 


* Tollen’s Ammoniacal Silver Nitrate Reagent.—This reagent is prepared by mixing equal 
volumes of a 10 per cent solution of silver nitrate in ammonia, and of a 10 per cent aqueous sodium 
hydroxide solution. ‘The ammonia solution used for dissolving the silver nitrate should be a 
mixture of one volume of the most concentrated aqua ammonia of commerce (sp. gr. 0.90) 
with one volume of water. The solution of silver nitrate in the diluted ammonia should always 
be kept in stock, but must not be mixed with the caustic soda until it is needed for an experi- 
ment, since the mixture on long standing deposits a highly explosive black precipitate. It also 
gives a black precipitate immediately, and without the addition of any reducing compound, 
when heated to boiling. It is a much more senstive reagent for aldehydes than a simple solu- 
tion of silver nitrate in ammonia. 

22 


NUMBEPED SPECIFIC TESTS OF GENUS I 23 


2. Shake in a three-inch test-tube 0.18-0.25 grm. of @-naphthol, 2 drops of concen- 
trated hydrochloric acid, and about 2.0 ce. of glacial acetic acid, until the naphthol is nearly 
all dissolved. Add one drop of the aldehyde and shake again. Heat at 50°-60° for about 
five minutes. Then boil for one minute. Cool and shake vigorously until a crystalline 
precipitate separates. Because of its tendency to form supersaturated solutions, this 
precipitate sometimes comes down slowly. Allow to stand until the precipitate has begun 
to settle. Filter through a small filter wet with glacial acetic acid. Wash with 1 ce. 
of cold glacial acetic acid. Bot with a mixture of 3 cc. alcohol and 1 cc. of water for half 
a minute or so. Most of the precipitate will remain undissolved. Cool thoroughly and 
Shake. Filter. Wash with 1 ce. of cold dilute alcohol (1:1). Dry 15-30 minutes at 100°. 

The product in this test—which is not directly applicable to very dilute solutions of © 
acetaldehyde—is ethylidene-f-dinaphthyl oxide, melting at 172.5°-173.5°. 


112. Acrolein. (Properties tabulated on p. 19.) 

The following tests for acrolein are to be applied to dilute aqueous solutions strong enough 
to possess a distinctly irritating odor. (Such a solution, for instance, as is obtained from 
the distillation of one drop of glycerine with acid potassium sulphate in Test 816-2.) 

1. Add 2 cc. of the acrolein solution to 5 cc. of the fuchsine aldehyde reagent pre- 
pared as described under Test I. (Addition of sodium acetate will never be necessary.) 
Allow the mixture to stand overnight at the ordinary temperature. It will then appear 
opaque by reflected light with a deep violet-blue color like cobalt glass. In very thin 
layers the color will be approximately VR. Add to the blue solution an equal volume 
of hydrochloric acid, sp. gr. 1.2. Within half a minute the color will change to an impure 
OYS2. Gradually dilute 2 cc. of this solution to 30 cc. with water. The color on _ 
dilution will change, passing through yellow-green and blue-green to about VB of the 
color standard (the comparison being made against a white background in a test-tube 
about 2 cm. in diameter). 

These color changes, collectively, distinguish acrolein from all other common volatile 
aldehydes, although the initial coloration alone is not characteristic. A dilute acetalde- 
hyde solution, such as would be obtained in applying the distillation test for glycerine 
(Test 816) to a drop of ethylene glycol, gives a quite similar coloration at the beginning 
' of the test, but this fades, sometimes almost to colorlessness, on standing overnight, while 
the surface of the solution becomes covered with a thin cantharides-green scum. At the 
end of the experiment when an acetaldehyde solution is used, after the treatment with acid 
and dilution with water, the final color will be an exceedingly pale tint of VR, having 
an intensity about half or one third of the VRT2 of the standard. 

2. Mix one drop of the acrolein solution with six drops of a cold saturated alcoholic 
solution of gallic acid, and dilute with water to 2 ce. Pour the mixture gently down the 
side of an inclined test-tube containing 3 cc. of pure concentrated sulphuric acid, in such 
a manner that the two liquids shal! not mix. Allow to stand for some minutes. <A very 
distinct red-orange (RO) ring will appear at the plane of contact between the liquids. 


113. Benzaldehyde. (Properties tabulated on p. 20.) . 

1. Dissolve one drop of the aldehyde in 12 cc. of 50% alcohol. Add one drop of pure 
phenylhydrazine and boil for half a minute. Cool. Shake well, and collect the bulky pre- 
cipitate on a small filter. Wash with 5 cc. of cold 50% alcohol. Redissolve the washed 
precipitate in 12 cc. of boiling 50% alcohol. Cool. Filter, and again wash with 5 ce. 
of cold 50% alcohol. Dry the well-drained precipitate on the opened filter for fifteen 
minutes in an oven at 100°. Determine its melting-point. 

The precipitate, benzalphenylhydrazone, is a crystalline white or faintly yellowish 
compound melting at 156° (uncor.) and changing in color to OT2— after exposure for one 
hour to diffuse daylight from a clear sky. The yield is very good. 


24 NUMBERED ALDEHYDE TESTS. 


2. In a small dry test-tube mix, in the order given, one drop each of melted phenol, 
the aldehyde, and concentrated sulphuric acid. Dissolve as much as possible of the 
colored product in 2-3 ce. of 10% sodium hydroxide solution by stirring with a glass rod, 
Benzaldehyde gives immediately a beautiful, intensely violet-red (VR) solution. 

3. Prepare a cold saturated aqueous solution of the aldehyde and $-naphthol by shaking 
together one drop of the aldehyde, a pinch of $-naphthol and 10 cc. of water. Filter, and 
pour 2-3 cc. of the clear solution down the side of an inclined test-tube containing 3 ce. of 
concentrated sulphuric acid. A violet-red (VRT1) colored zone will appear at the plane 
of contact between the acid and aqueous layers. 


114. Formic Aldehyde. (Properties tabulated on p. 19.) 


1. Mix one drop of a one-half per cent aqueous solution of resorcine with 1 cc. of a 
dilute aqueous solution of the aldehyde of such a concentration (about 1:500) that the 
irritating odor of the aldehyde is just barely perceptible in the cold, though rather un- 
pleasantly strong when the solution is heated to 100°. Allow the mixture to flow gently 
down the side of an inclined test-tube containing 3-5 cc. of pure concentrated sulphuric 
acid. Impart a gentle rotary motion to the liquids by cautiously swaying the lower end 
of the tube through a circle about a decimeter in diameter in such a manner as not to cause 
the disappearance of the two layers. 

If formic aldehyde is present ared (R) ring, slightly tinged with violet, will soon appear. 
Above this ring a lght flocculent precipitate, at first nearly white on its upper surface, 
and red-violet beneath, but soon changing to flocks that are red (R) throughout, will be 
seen eas in the aqueous upper layer. 

2. Repeat part I of the test, substituting six drops of a cold saturated alcoholic solu- 
tion of gallic acid for the resorcine. A pure blue (B) ring will be formed. 

[In either of the preceding color tests it would be a serious mistake to employ too 
concentrated aldehyde solutions. Such solutions yield deep-colored precipitates that 
obscure the purer and more characteristic hues that it is desired to produce.] 

3. (Applicable to concentrated aqueous solutions like the commercial “formalin”’.) 

Place in a test-tube three drops of the solution, 3 cc. of dilute alcohol (1:2), 0.04— 
0.06 gram of #-naphthol, and three to five drops of concentrated hydrochloric acid. Boil 
gently until the liquid fills with an abundant precipitate of small white needles. Filter 
while hot. Wash with 1 cc. of dilute alcohol (1:2). Boil the precipitate with 4 cc. of 
dilute alcohol (1:1). (It is not necessary that all should dissolve.) Cool, and filter off 
the precipitate. Wash with 1 ec. of dilute alcohol (1: 1). Dry on porous tile in a warm 
place and determine the melting-point. 

Methylene-di-8-naphthol, the product, forms white needles, which, when the temperature 
in the neighborhood of its melting-point is raised at the rate of 1° in 15 seconds, begins to turn 
brown at 180°. It melts with decomposition to a brown-red liquid at 189°-192° (uncor.). 

The directions for part (8) of this test are specially intended for use with solutions 
containing 30-40% of formic aldehyde, but they become applicable to much weaker solu- 
tions, if the quantity of the aldehyde solution taken in such cases is proportionately increased. 
In working with a 10% solution, for example, ten drops instead of three should be used. 
A moderate excess of the aldehyde produces no injurious results. | 

4. The p-nitrophenylhydrazone of melting-point 181—2° is recommended by Bamberger 
(Ber., 32, 1807) as an excellent derivative for formic aldehyde. 

115. Furfurol. (Properties tabulated on p. 20.) 


1. Mix in a dry test-tube one drop of the aldehyde and two drops of pheayihyaraae 
Dissolve the pasty reaction product in 3 cc. of boiling 50% alcohol. Cool well in running 
water, and shake until the precipitate, which often appears at first in an amorphous con- 
dition, separates in pearly crystalline scales. Collect on a small filter. Wash with 5 ce. 


NUMBERED SPECIFIC TESTS OF GENUS I. 25 


of a cold mixture of two volumes of water and one of strong alcohol. Transfer the pre- 
cipitate to a test-tube and redissolve in 5 cc. of a boiling mixture of one volume of strong 
alcohol and two of water. If a few dark-colored droplets should separate at this point, 
allow them to settle, and decant the clear hot solution into another tube. Cool and shake 
the solution until pearly scales are again separated. Collect on a small filter and wash 
with 5 cc. of a cold mixture of two parts of water and one of strong alcohol. Drain. Dry 
in an oven at 85°, and then determine the melting-point. 

Furfurolphenylhydrazone, the product of this test,,melts at. 97° (uncor.). The crystals 
have a pale-yellow color and a conspicuously pearly lustre. 

2. Boil in a test-tube a mixture of one drop of the aldehyde and 2-3 cc. of water. 
Moisten a strip of paper with a mixture of equal parts of aniline and glacial acetic acid,. 
removing any excess of the mixture with blotting-paper. Hold a roll of test-paper in 
the steam issuing fromthe tube. If the furfurol is present, the paper will be immediately 
colored a bright hight red (RTI). The test is simple and delicate. 


CHAPTER IV. 
GENUS II. CARBOHYDRATES 


OF 
SUBORDER I, ORDER I. 


(Colorless Compounds of Carbon, Hydrogen, and Oxygen.) 


This genus includes all the carbohydrates treated in the work, but no glucosides. The 
species described when pure are all solid at the ordinary temperature. 


GENERIC TEST II. 


THIS TEST CONSISTS OF TWO PARTS, THE MOLISCH CARBOHYDRATE REACTION, 
AND THREE SUPPLEMENTARY TESTS. APPLY THE MOLISCH REACTION 
FIRST; THEN, IF THE RESULT SHOULD BE NEGATIVE, OMIT THE SUPPLE- 
MENTARY TESTS. THE REASON FOR APPLYING THE LATTER, WHEN THEY 
ARE REQUIRED, IS TO EXCLUDE CERTAIN SPECIES OF OTHER GENERA WHICH 
GIVE COLORATIONS IN THE MOLISCH REACTION, AND MIGHT CONSEQUENTLY 
BE MISTAKEN FOR CARBOHYDRATES. 


The Molisch Carbohydrate Reaction.*—Place about 5 mgr. of the substance 
with 10 drops of water in a small narrow test-tube, and mix with 2 drops of a 10 per 
cent chloroform solution of a-naphthol. Allow 1 ec. of pure concentrated sulphuric 
acid to flow slowly from a pipette down the lower inclined side of the tube, so that 
the acid may form a layer beneath the aqueous solution without mixing with it. 
If a carbohydrate is present, a red ring will appear within a few seconds at the line 
of separation between the two layers. The color soon changes on standing or shaking, 
a very dark-purple solution being formed. Shake, and allow to stand for one or 
two minutes; then dilute with 5 cc. of cold water. In presence of a carbohydrate, 
a dull-violet precipitate will immediately appear. Addition of an excess of strong 
ammonia will change the color to a rusty-yellowish brown. Any substance that 
gives the dull-violet and rusty-brown precipitate, as well as the purple coloration, 
under the circumstances described, may be assumed to be a carbohydrate. 

Observations.—On account of the delicacy of the Molisch Reaction it is very 
essential that the substance examined shall be entirely free from all traces of filter- 
paper, particles of woody fibre, or dust. The purity of the reagents employed 
should also be placed beyond question. The presence of nitrous acid in the sul- 
phuric acid is specially objectionable. The reagents may be tested by shaking 
one drop of a-naphthol solution with ten drops of water and 1 cc. of concentrated 
sulphuric acid. The mixture should be of a golden-yellow color. If dark green, 
the reagents are not sufficiently pure. The naphthol solution does not keep well, 
and so should not be prepared in large quantities. 


* Modified from Molisch, M. 7, 198 (1888). 
26 


GENUS II. CARBOHYDRATES, 27 


The immediate cause of the colorations observed in the Molisch Reaction is 
supposed to be the formation of an unstable condensation product of furfurol and 
a-naphthol. 

The Supplementary Tests.—(1) Test the reaction of a little of the substance, 
which has been dissolved or suspended in powdered form in a few drops of water, 
with litmus. If the reaction is distinctly acid, the compound is not a carbohydrate. 

(2) Place about 5 mgr. of the substance in a small test-tube, cover with 10 drops 
of water, and then mix with 1 cc. of concentrated sulphuric acid. If a red or purple 
coloration, or indeed any coloration other than a yellow or brown to black, makes 
its appearance, the compound is not to be sought among the carbohydrates. 
(This test results in the exclusion of several glucosides like salicin and coniferin.) 

(3) Add one drop of a one tenth per cent ferric-chloride solution to 1 ce. of 
a 1 per cent aqueous solution of the substance; or if the latter is very insoluble, 
to its cold saturated aqueous solution. Unless the solution remains colorless, or, 
at most, shows a pale-yellow or orange-yellow coloration, the compound is not to 
be looked for in this genus. (This test excludes certain glucosides like arbutin 
and esculin.) 


SUBDIVISIONS AND CONTENTS OF GENUS II. 


The principles guiding the selection and arrangement of species in this genus 
differ materially from those followed in the case of other genera. The carbohy- 
drates that have been obtained in a pure condition up to the present time are all solids. 
The genus therefore contains only a single “ Division,’ which is subdivided into two 
“Sections,” and several small “Subsections,” whose relations to one another will be readily 
understood from an inspection of the tables. Section 1 includes all species giving clear 
solutions in less than ten parts of cold water. It contains all the sugars, monosaccharide 
and polysaccharide. Many, but not all of them, have a sweet taste. The species of Sec- 
tion 2 are either insoluble in ten parts of cold water, or dissolve to solutions that remain 
opalescent or turbid after repeated filtration. This is the section of starch, glycogen, 
and cellulose. The members of both sections are colorless, odorless, and neutral towards 
indicators. 

It will be noticed that the number of species described is comparatively small. The 
names of a majority of the rare synthetic sugars, such as the glucoses and taloses, l-glucose 
and 1|-fructose, the heptoses, octoses, and nonoses, are lacking, as are also many of those 
of the less accessible natural carbohydrates. The cause of these omissions is the nature 
of the scheme of analytical procedure adopted. This is simple and systematic, but of such 
a character that the position of every species described had to be determined by actual 
experiment. It will not be amiss to remind the reader that the direct application of the 
tests recommended in this chapter to unknown mixtures is not allowable. 

Generic. Characteristics.—The carbohydrates seldom melt sharply, because fusion 
is nearly always preceded by slight decomposition. Their melting-points are accordingly of 
minor importance as specific properties, and worthless as indications of chemical purity. 
When determined they should be observed by the capillary-tube method (cf. p. 220) in 
a bath whose temperature is rising somewhat rapidly. The instability of the sugars 
towards heat is further manifested by their tendency to pass into the state of uncrystallize- 
able syrups when their solutions are concentrated by boiling down under the ordinary 
atmospheric pressure. 

The specific rotations of the soluble carbohydrates cover a wide range in their values ; 
are the most characteristic of their physical constants; and will usually be determined 


28 GENUS II. CARBOHY DRATES 


in any laboratory that is equipped with the requisite apparatus. The deficiency of many 
laboratories m. this respect is the only reason for not employing the specific rotation as 
the chief means for fixing the arrangement of the soluble carbohydrate species within 
their “sections.”’ The description for any sugar.in the tables is always for the more com- 
mon of the two optical isomers bearing the name. The description for the ° ‘optical anti- 
pode,” if it were given, would be the same as that for its isomer, except that the. specific 
rotation would have the opposite algebraic sign. 

Many of the soluble carbohydrates reduce Tollen’s ammoniacal silver nitrate reagent 
(cf. p. 22) in the cold, and Fehling’s solution (cf. Test 202) on heating: ‘but none of 
them, even such as have been shown to contain the aldehydic grouping, redden’ ret fuch- 
sine siddlngde reagent of Test I. 

Heated with normal potassium hydroxide under the conditions: preseribed, for the 
saponification of ‘esters (cf. Test. V), some carbohydrates are rapidly attacked, giving 
dark brown or black solutions and neutralizing much alkali; others, like cane-sugar, remain 
practically unchanged after long-continued treatment.. Some of the reactions of the group 
that have been found most valuable for diagnostic purposes, such as those leading to the 
formation of osazones, furfurol, etc., and the use of Fehling’s solution, are described in the 
numbered reactions ieatvany on page 32. 


COLORLESS COMPOUNDS CONTAINING C, H, AND 0 [SUBORDER I OF ORDER I} 
GENUS II, CARBOHYDRATES. 


SECTION 1. 


CARBOHYDRATES SOLUBLE IN LESS THAN TEN PARTS OF WATER AT 20°, GIVING 
SOLUTIONS WHICH ARE NOT OPALESCENT AFTER FILTRATION. 











SECTIONAL PROCEDURE.—Apply Test 201 (“‘ Rapidity of Osazone Formation’’) to 
0.1 grm. of the substance.—-Then: (1) if a white crystalline precipitate appears within less 
than one minute, see Subsection A; (2) if no precipitate separates from the hot solution 
within twenty minutes, see Subsection B; (3) if a yellow or orange-yellow precipitate sepa- 
rates within less than twenty minutes, see Subsection C. 


Subsection A. [Test 201 gives a nearly white precipitate within.1 minute. ] 


{ d-Mannose, C,H,,0,.—Hard amorph. mass, or pr. fr. 90% alc.; s. 0.4 pt. c. aq.; d.s. ¢./alc.; 
i. eth—_{a]p = + 14-4°.—Taste sweet.—Reduces Fehling’s sol. (Test 202).—Test 201 gives 
a nearly white cryst. ppt. of the phenylhydrazone after 4 min. heating, which after recryst. 
fr. boiling aq. melts at 195°-200° (r. h.)! (The last test is characteristic.) 


Subsection B. [Test 201 gives no precipitate after heating for 20 min.] 
SUBSECTIONAL PROCEDURE.—Test with Fehling’s solution by Test 202. If a 
heavy red precipitate is obtained, see maltose, lactose, and dextrin; if none appears, or if it 
is yellowish and very scanty, see saccharose, raffinose, and gum arabic. 

+ Maltose, C,,H,.0,, + H,O.—Fine white ndl., losing aq. at 100-10°._V.s.c.aq.; v.d.s. ¢. ale.— 
Tastes as sweet as cane-sugar.—{a]p = +137-7°.—In Test 201 no osazone separates fr. the 
sol. while hot, even after 2 hours’ heating.—Oxidation by Test 205 gives saccharic ac., but 
no mucic ac. 

} Lactose (Milk-sugar), C,,H,.0,, +H,O.—Large, hard, white cryst., losing aq. at 130°; turns 
yellow abt. 160° and melts abt. 200° d.—8. 6 pt. ¢., or 24 pt. h. aq.; 1. ale. or eth—{[a]p= 
‘“+52-5°.—In Test 201 no osazone separates fr. the h. sol. even after 2 hours’ heating. 
Taste only faintly sweet—Oxid. by Test 205 gives mucic ac, and saccharic ac. 


+ “ Dextrin.”—Although commercial dextrin is not a true chemical species, being a mixture of 
several hydrolytic decomposition products of starch, its practical importance renders some 
‘mention of its properties and reactions in this place desirable. It is usually a white or 
slightly brownish powder of insipid mucilaginous taste; v. 8. In h. aq. and for the most 

art also in c. aq ; though in the latter case the sol. is apt to be somewhat milky or turbid. 

est 201 usually gives no ppt. of osazone in the hot solution after 20 minutes.— Unless 
unusually free from reducing sugars, Test 202 with Fehling’s sol. gives a red ppt.—_{a]o>= 
+ 200° (approximately).— Unless so much starch is present as to give a blue color, a very 
dilute sol. of I in KI produces a strong brown coloration. Unlike gum arabic it does not 
give Test 204 with phloroglucine.—For additional tests cf. Allen, vol. 1, p. 419. 


Saccharose (Cane-sugar), C,,H,,0,,.—Colorless monoclinic cryst. s. in 4 pt. c. aq.; d.s.c¢. alc.; 
! 100 cc. c. abs. methy] ‘alc. dissolve 0-4 grm.—M. p. abt. 160°-70° d.—_{a]p>= + 66°-5. Taste 
very sweet.—In Test 201 the yellow osazone ppt. begins to separate fr. the hot sol. if the 
heating is continued for abt. 30 min.—Oxid. by Test 205 gives saccharic ac., but no mucic ac. 


+ Raffinose, C,,H,,0,,+5H,0.—Ndl., losing all aq. at 110°; when anhydrous melts at 118°-19°.— 
S. in 7 pt. aq. at 20°; 100 cc. abs. methyl alc. dissolve 9-5 grm. of the anhydrous sugar 
(dif. fr. saccharose); alm. i. c. ethyl alc.—Taste not noticeably sweet.—[a], = + 104-5°. 
In Test 201 the yellow osazone does not separate fr. the hot sol. unless the heating is con- 
tinued for abt. 60 min—Oxid. by Test 205 gives both saccharie and mucic acids. 


f Gum Arabic.—Although not a true chemical species, this substance gives many of the reac- 
tions of this section and may be sometimes sought at this point. It consists in part of 
calcium arabate, and is a hard gum having a fairt odor and insipid mucilaginous taste. tt 
dissolves slowly in about 2 pts. of c. aq. to a thick transparent mucilage, but is i. in alc. 
It gives Generic Test II, and Specific Tests 203 and 204.—It gives no osazone ppt. 
in the h. sol. after 20 min. heating in Test 201, and gives little or no ppt. in Test 202 
with Fehling’s sol —Oxid. by Test 205 gives mucic ac_—Ammonium oxalate and ammonia 
ppt. calcium oxalate fr. the aq. sol. For other tests cf. Allen, vol. 1, p. 426. , 

9 


30 GENUS II, CARBOHYDRATES. SECTION 1. 


Subsection C. [Test 201 gives a yellow or orange- yellow precipitate from the hot solution 
within 20 minutes. All species also give a heavy red precipitate with Fehling’s solution in 
Test 202. | 


SU BSECTIONAL PROCEDURE.—Apply Test 203. If no test for furfurol is obtained, 
see dextrose and galactose. If, on the other hand, furfurol is formed, apply Test 204 with 
hydrochloric acid and phloroglucine. If the precipitate from Test 204 is of a dark-purple 
color, see arabinose and xylose; if brown, see levulose, sorbinose, and rhamnose. 

{ d-Glucose (Dextrose or Grape-sugar), C,H,,0,.—Ndl. or crusts fr. ale. (m. p. 146°), or in tbl. 
w. 1H,O fr c. aq. (m. p. abt. 85°-90°).—Anhydrous dextrose is s. in 1-2 pt. aq. at 17-5°; 
d. s. c. 90% alc., but v. s. h.; i. eth—{a]p>=+52-8°. Tastes half as sweet as cane-sugar. 
In Test 201 a heavy yellow ppt. of the osazone [m. p. 204°—-5° (r. h.)] separates suddenly 
from the hot sol. after abt. 4-5 min. heating! ‘Test 205 gives saccharic but no mucic ac. 

+ d-Galactose, C,H,,0,.—Small hexagonal tbl. fr. abs. ale., m. p. 168° (r. h.); cryst. fr. aq. w. 
1H,0O, m. p. abt. 118°-20°. E. s. c. aq.; d.s. c. ale—la]>=+80-3°. Tastes about as 
sweet as dextrose.—Test 201 gives a heavy yellow to orange-yellow ppt. of the osazone, 
m. p. abt. 196° (r. h.), separating fr. the hot sol. after about 15-19 min. heating! Oxid. by 
Test 205 gives mucic ac. ! ‘ | 

+ 1-Arabinose, C,H, ,0;.—Pr. fr. alc., m. p. abt. 160°. V.s. c. aq.; v.d.s. ale.; i. eth—{a])= 
+104°-5°. The orange-yellow osazone, m. p. 160°, separates fr. the hot sol. in Test. 201 
after abt. 10 min. heating; unless the sugar is very pure the osazone often separates in 
part in the form of brownish-yellow oily drops. Test 204 gives a purplish-black ppt.— 
Arabinose is best distinguished from xylose by preparing the p-bromphenylhydrazone as 
described by Fischer [Ber. 27, 2491]. 

} Xylose, C,H,,0;—Ndl. v. s. c. aq.; alm. i. c. alc. or eth.; m. p. abt. 150°-3°._{a], = + 18.7°. 
—The orange-yellow osazone, m. p. abt. 160°, separates fr. the hot sol. in Test 201 after 
abt. 7 min. heating. Test 204 gives a purplish-black ppt.—t Xylose may be quite easily 
distinguished from arabinose by conversion into cadmium xylonate by the method of Ber- 
trand [Bull. Soc. [3], 5, 556]. 

+ d-Fructose (Levulose), C,;H,,0,.—Somewhat hygroscopic cryst. or crusts fr. ale.; m. p. 94°! 
Also in ndl. w. $H,O fr.aq. V.s.aq.; s. 5 pt.c. abs. alc.; s. eth./—_la]p=—90-2°. Tastes 
as sweet as cane-sugar.—A heavy yellow ppt. of the osazone, m. p. 204° (r. h.), separates 
from the hot sol. after abt. 2 min. heating in Test 201.—Gives dark, rusty-brown ppt. in 
Test 204. 

{ Sorbinose, C,H,,.0,.—Rhombic cryst. s. in 4 pt. c. aq.; d.s.h. ale.; m. p. 164°!_(a], = —43-4°. 
Tastes as sweet as cane-sugar.—The yellow osazone, m. p. abt. 164° (r. h.), separates from 
the hot sol. in Test 201 after abt. 34 min. heating; it usually separates partly in the form 
of oily drops, but is easily purified by recryst. from a mixture of acetone and ether.—Test 
204 gives a dark, rusty-brown ppt. 

{ Rhamnose (Isodulcite), C,H,.0,+ H,O.—Hard, glassy cryst. fr. aq. or alc., m. p. below 100°. 
S. in 2 pt. c. aq.; v. d. s. c. ale—[a},=+9-43°. Tastes faintly sweet.—The osazone 
separates from the hot sol. in Test 201 after abt. 9 min,, as a heavy yellow ppt. (ndl. fr. 
bz., m. p. abt. 180° d.). 


GENUS II, CARBOHYDRATES. SECTION 2. 31 


SECTION 2. 


CARBOHYDRATES WHICH EITHER ARE NOT SOLUBLE IN TEN PARTS OF COLD 
WATER, OR WHICH DISSOLVE, GIVING SOLUTIONS THAT REMAIN STRONGLY 
OPALESCENT AFTER FILTRATION. 





{ Starch, (C,H,,0,)2.—Ordinary air-dried starch is a white, tasteless powder, containing about 
18% of water. Under the microscope it is seen to consist of granules showing concen- 
trically stratified structure whose size and shape are often characteristic of the plant by 
which they were produced. (For details concerning the microscopic identification, cf. 
Allen, vol. I, p. 405.)—Starch is undissolved and unacted upon by c.aq., alc.,or eth. <A 
few cgrms. of the powder rubbed to a thin cream with cold water and then gradually stirred 
into 100 cc. of boiling water quickly dissolve to a nearly clear solution. This solution, after 
being cooled, gives a white ppt. with tannin or with much alcohel.—A few drops of a very 
dilute solution of I in KI gives an intense deep-blue coloration: The blue solution is tem- 
porarily decolorized by warming, or permanently by traces of free alkali. In an alkaline 
solution the color may be restored by acidifying with dil. HCl. (This characteristic color 
reaction will be masked by the presence of much erythrodextrine, which gives a deep red- 
dish-brown color with the reagent, unless care is taken to use a very weak iodine solution, 
and to add it gradually.) 

f Cellulose, (C,H, ,0,)z.—A white, tasteless, amorphous solid, insoluble in water and all ordinary 
organic solvents, either cold or hot, but dissolving in Schweitzer’s reagent, 1.e., in ammonia 
that has been saturated with cupric hydroxide (obtained by precipitating a cold solution 
of copper sulphate with an excess of caustic soda and washing the ppt. well with cold water), 
giving a viscid solution, from which it may be reprecipitated in a flocculent state by neu- 
tralization with acid.—After a few seconds’ immersion in a cold mixture of 2 vol. conc. 
H,SO, and 1 vol. aq., cellulose assumes a deep-blue color if wet (either immediately or after 
hastily rinsing with cold water), with a few drops of 2% iodine solution containing KI. 
[Unless it has been previously treated with such reagents as ZnCl, or conc. H,SQ,, cellu- 
lose is not colored blue by the iodine solution. ] 

{ Inulin, C,,H,.0.,, (dried at 130°).—A tasteless white powder; m.p. 178°d. Under the micro- 
scope it is seen to consist of spheroidal cryst. aggregates. Alm. i. c. aq.; v. 8s. h. aq. giving 
clear solution which shows tendency to remain supersaturated for a long time; alm. 1. alc. 
[a]> = —39-5°. Easily hydrolyzed by h. dil. HCl, chief product being levulose. Does not 
reduce Fehling’s sol. (Test 202). Test 201 gives a yellow osazone which begins to sep- 
arate from the hot sol. after abt. 25 min. heating. Gives no coloration with dil. I sol. 

} Glycogen, C,H,,0,,—White amorphous powder, m. p. abt. 240°. E. s. c. aq. to intensely 
yoogen, ©4195 phous p } . 
opalescent sol.! This opalescence is not destroyed by repeated filtration, but is removed 
by addition of acetic acid. I. ale—{a]o>=198°.—Test 202 w. Fehling’s sol. gives no ppt. 
Test 201 gives no ppt. of osazone after heating for one hour. 

f{ Commercial Dextrin.—Cf. Subsection B. (Filtered sol. in c. aq. often somewhat milky; 
usually reduces Fehling’s sol.) 


SECTIONAL AND SPECIFIC CARBOHYDRATE TESTS. 


[TESTS 201-300.] 


201. Osazone Precipitation. 

Place in a dry test-tube having an internal diameter of 13 mm., 0.100 grm. of the 
carbohydrate, 0.200 grm. of pure phenylhydrazine hydrochloride* (cf. Note below), 0.300 
erm. crystallized sodium acetate, and 2.00 cc. of distilled water. The errors in 
measurement should not much exceed 1: per cent. Close the tube loosely with a cork 
stopper to prevent evaporation, and stand it upright in a tall narrow beaker containing 
two or three inches of water that is already briskly boiling. Note the exact moment of 
immersion. Shake the tube occasionally without, however, removing it from the beaker. 
If a precipitate finally separates, note the number of minutes that have elapsed up to 
the moment; of its appearance. The precipitate usually separates out quite suddenly, so 
that duplicate experiments will generally give results that agree within about half a minute. 
Note also whether the precipitate is white, yellow, or orange-yellow, and whether it is 
crystalline, flocculent, or tends to rise to the surface in oily drops. The properties 
enumerated are all used either as subsectional or as specific tests in the tables. 

If a melting-point of the osazone is desired, and it will often be found an important 
specific constant, cool the hot solution; collect the precipitate on a very small filter; wash 
with a little cold water; dissolve in the smallest possible volume of boiling 50 per cent 
alcohol, and filter hot. If the quantity of precipitate which separates on cooling permits, 
recrystallize once more in the same manner. Dry the precipitate, first on a bit of porous 
tile, or between filter-papers, and finally at 100°, and determine the melting-point in a 
bath whose temperature is rising rapidly. 

The fact that the rate of osazone formation 1s very shes: for the various sugars 
was first clearly indicated by Marquenne,t but seems not to have been hitherto very gener- 
ally known or taken advantage of by analysts. The conditions for the test in its present 
form are so planned that the monosaccharide sugars (the pentoses and hexoses) all give 
precipitates in from thirty seconds to twenty minutes. Of the polysaccharide sugars, 
some, like maltose, give products which do not separate until the hot solution is cooled; 
others, like saccharose, are gradually hydrolyzed to monosaccharides, which then oe 
the corresponding osazones, but naturally require a longer time for the reaction than 
when the simple sugar was originally present. The times given in the table for the 
appearance of precipitates in different cases are based on experiments by several observers, 
and except for xylose and mannose, several. distinct preparations were used for examina- 





* [Note on Phenylhydrazine Hydrochloride.—This salt, unless very pure and dry, rapidly 
decomposes and darkens on keeping. Only a perfectly white and dry salt should be used for 
the foregoing test. Although the commercial hydrochloride often fails to meet these require- 
ments, a very satisfactory reagent is easily prepared by dissolving a light-colored sample of 
phenylhydrazine in twelve volumes of strong alcohol, and then precipitating out the hydro- 
chloride by the addition of a sufficient excess of the most concentrated hydrochloric acid. Wash 
the precipitate thoroughly on a suction-plate, first with alcohol and ether, and then with ether, 
until it is snow-white throughout. Dry on filter-paper in a warm place ‘for half an hour, and 
then for at least an hour at 100°. Such a preparation, if white at the start, may be preserved 
for many months if placed in a tightly stoppered bottle, and not freely exposed to the light]. 

+ Compt. rend. 112, 799. 


32 


NUMBERED SECTIONAL AND SPECIFIC. TESTS OF GENUS II. 33 


tion.’ Variations of a minute or two from the stated time-values will occasionally occur 
however, and this should not be overlooked when it is a question of selecting between 
two species whose values lie. close together. The precipitates are all phenylosazones, 
1.¢., di-phenylhydrazones, except that from mannose, which is a simple phenylhydrazone, 
and is easily distinguished from’ its associates in being white instead of yellow. 


202. Reduction of Fehling’s Solution. 


__ Add eight drops of Fehling’s Solution * to a solution of approximately 0.03  grm. 
of the carbohydrate in 3 ce. of water. Boil for two minutes if no precipitate appears 
before. 

Arabinose, xylose, rhamnose, mannose, glucose, galactose, fructose, sorbinose, malt- 
os¢, and lactose give almost immediately a red to yellow-orange precipitate of cuprous 
oxide on heating. Inulin, raffinose, saccharose, and gum arabic give only a scanty yellowish 
turbidity after two minutes’ boiling. Glycogen, starch, and cellulose give no precipitate 
after two minutes’ boiling. The behavior of commercial dextrin is quite variable. 


203. Aniline Acetate Test for Carbohydrates giving much Furfurol with 
Acid. 


Dissolve 0.3-0.4 grm. of the carbohydrate in 5 cc. of hydrochloric acid prepared by 
mixing one volume of an acid of sp. gr. 1.20 with three volumes of water. Boil for one 
minute. Then insert a cylindrical roll of freshly prepared aniline-acetate paper,t two 
inches long, for half its length into the upper end of the test-tube from which the vapors 
of steam and furfurol are issuing. Continue the boiling one minute longer if necessary. 

Certain carbohydrates of Section 1, Subsection C, viz., arabinose, xylose, rhamnose, 
fructose, and sorbinose, give enough furfurol when thus treated to communicate a bright 
pink color to the test-paper. The other carbohydrates of this subsection do not occasion 
noticeable colorations. The coloration sometimes appears in streaks and blotches, but 
often covers the entire surface of the paper. 


204. Color Reactions with Phloroglucine. 


Boil 3 ce. of the phloroglucine reagent described below {t with about 0.03 grm. of 
the carbohydrate in a small test-tube. Note the color when boiling is about to begin. 
Continue to boil until the color ‘darkens very considerably, and the solution begins to 
appear slightly turbid. This will occur within a minute from the moment when boiling 
begins. Pour the hot solution without delay onto a wet filter, and rinse the scanty pre- 
cipitate with a little cold dilute alcohol. Note-the color of the precipitate while moist; 
it is the most characteristic result of the test. 

This test is used to distinguish between certain carbohydrates of Section 1, Subsec- 
tion C. The first coloration on heating with arabinose and sylose is a pure red to violet-red 


* Preparation of Fehling’s Solution.— Dissolve 34.64 grms. of pure crystallized copper sulphate 
in distilled water, and dilute the solution to 500 cc. Dissolve 70 grms. of caustic soda of good 
quality, and 180 grms. of the best crystallized Rochelle salt (potassium-sodium tartrate) in 
about 400 cc. of water, and dilute to 500 cc. Keep the solutions in separate bottles, and prepare 
the Fehling’s solution fresh before each series of experiments by mixing the two together in equal 
volumes. 

+ Preparation of Aniline Acetate Paper.—This is prepared as required for use by wetting 
strips of thick filter-paper in a mixture of 5 cc. of aniline and 10 cc. of 50 per cent acetic acid, 
pressing out all excess of the solution between blotting-papers. It should be used while still 
slightly moist. Xylidine-acetate paper, which has also been recommended by Schiff [A. 239, 
380] for the detection of furfurol, is somewhat more sensitive than the paper prepared from 
aniline acetate. The latter is, however, thoroughly satisfactory for use in the present test. 

{ Preparation of Phloroglucine Reagent—This reagent is made by shaking an excess of 
powdered phloroglucine with a mixture of equal volumes of concentrated hydrochloric acid and 
water, until the solution is saturated. The clear solution, unless freshly prepared, is slightly 
yellow, but remains serviceable for many months and should be kept in stock. 


34 NUMBERED CARBOHYDRATE TESTS. 


(R-VR), which rapidly intensifies and darkens. The color of the precipitate varies 
according to the duration of the boiling from a very dark purple (VRT2 or RVT2) to black 
if the boiling is too long continued. With rhamnose, fructose, and sorbinose the first colora- 
tion is yellow-orange (YO), quickly passing through dark orange to dingy brown. The 
precipitate is of a rusty brown, or dark broken shade of yellow-orange or orange (YO or 
O), which will easily be changed to a dull black if the boiling is too long continued. 


205. Oxidation to Mucic or Saccharic Acid. 


Galactose is the only hexose yielding mucic acid on oxidation with dilute nitric acid, 
and glucose the only one, with the exception of the artificial sugar gulose, that gives sac- 
charic acid. The reaction has the merit of being applicable to carbohydrate mixtures, 
as well as to the simple sugars and their polysaccharide and glucoside derivatives. Several 
grams of the carbohydrate must be oxidized to ensure satisfactory results if saccharic 
acid isto be sought. The method is fully described by Gans and Tollens, A. 249, 215 
(1888), and more briefly by Allen, Vol. I, p. 270.. A close adherence to all details given 
in these directions is necessary. 


CHAPTER V. 
GENUS III. ACIDS 


OF 
SUBORDER I, ORDER I. 


(Colorless Compounds Containing Carbon, Hydrogen, and Oxygen.) 





This large and important genus includes all non-aldehydic species of the suborder 
that contain the carboxyl radical, together with a few acid anhydrides and easily sapon- 
ified esters that show the same behavior as acids when titrated with decinormal alkali by 
the method of Generic Test III. Many compounds whose solutions in water or alcohol — 
redden blue litmus, including a few like “carbolic acid,” are popularly known as acids, 
but are too feebly acidic to meet the requirements of this test. Such species are accord- 
ingly treated elsewhere, most of them in Genus IV. 


GENERIC TEST III. 


APPLY PROCEDURE 1 OF THIS TEST FIRST TO EVERY COMPOUND, SOLID OR LIQUID, 
REGARDLESS OF SOLUBILITY. APPLY PROCEDURE 2 ONLY TO SOLID COM- 
POUNDS INSOLUBLE IN WATER WHICH IT IS FOUND DO NOT TITRATE LIKE 
ACIDS IN PROCEDURE 1. 


PROCEDURE 1, 
(Titration in Water.)* 


Weigh out accurately about 0.10 grm. of the dry substance, finely powdered 
if it is a solid, into a beaker of 50 cc. capacity. Add 10-15 cc. of cold distilled 
water, and one drop of a solution of phenolphthalein made by dissolving one part 
of the indicator in three hundred parts of 50 per cent alcohol. Place the beaker 
on a sheet of white paper, and titrate cautiously with decinormal soda or baryta 
until the pink color produced by an excess of one drop of the alkali, after exact 
neutralization, persists for more than one minute when the solution is constantly 
stirred. 


PROCEDURE 2. 
(Titration in Alcohol.)* 
If less than 2 cc. of the alkali were required for neutralization in Procedure 1, and 


if the substance at the same time did not go into solution, and is a solid, repeat the 
titration, replacing the distilled water by about 25 cc. of strong alcohol of the best 





* Shorter Alternative Procedure.—Whenever the substance is not very valuable 
and is not believed to be an acid, it is allowable to take a small unweighed pinch, 
or three drops (about 0.1 grm.) of the substance for the titrations. If not more 
than three or four drops of alkali gre neutralized, or if the color transition in the 
end reaction is not ‘‘sharp,” the time otherwise required for weighings and calcu- 
lations will be saved. 

35 


36 GENUS III. ACIDS. 


quality, using three or four drops of phenolphthalein instead of one, and disregard- 
ing any precipitate that may form.—[The best commercial alcohol usually reacts 
acid. This acidity should be exactly neutralized by alkali in each experiment 
before adding the substance to be titrated.] 

Any compound that consumes more than 2 cc. of decinormal alkali in either 
titration, and that also gives a sharp and normal color transition in the end reaction, 
should be sought in Genus III. The sharpness of the color transition, and the 
alkali consumption, are phenomena of codrdinate importance. The phrase ‘‘ sharp 
color transition in the end reaction”’ is here used with the restricted, definite mean- 
ing given to it in the explanatory observations below. Any compound that yields 
a solution at the end of the titration that has a pronounced color other than pink 
is likely to be a species of Genus IV. 

Observations on Generic Test III.—Never titrate hot solutions nor substitute 
some other indicator for phenolphthalein. 

Never omit to reduce the substance to a uniformly fine powder before beginning 
a titration, unless it is known in advance that it dissolves quickly in cold water. 
All but the weakest and most insoluble acids may, with a little patience, be success- 
fully titrated without the use of alcohol if this injunction is observed and the 
suspended powder is persistently stirred. Even terephthalic acid, which is said 
to require 67,000 parts of cold water for solution, gives little trouble. But if an 
acid is at once almost absolutely insoluble and very weak, like stearic and other 
higher solid fatty acids, an aqueous suspension will not neutralize the alkali, and 
the use of alcohol becomes indispensable. The sharpness of the color change at 
the end of a titration is usually more striking in aqueous than in aicoholic solutions. 

The end reaction in Generic Test III may be defined as beng sharp in the sense 
intended, when a single drop of decinormal alkali, added at the rvment when the solution 
is exactly neutral but still colorless, suffices to develop a full strong pink color which 
is not greatly intensified if the quantity of jree alkali 7g vncreased. Some phenols, 
$-diketones, and similar compounds, consume more than 2 cc. of the alkali before 
the appearance of a pink color, but they may be distinguished from the species 
of Genus III by the lack of sharpness in their ‘‘@nd reactions.” That is to say, 
an excess of a single drop of the alkali, added at the end of the titration of such 
a substance, produces only an almost imperceptible pinkish coloration, that then 
gradually increases in intensity when more alkali is added. There is no abrupt 
transition such as is observed in titrating a true acid whose salts are not hydrolyzed 
in solution. The quantity of alkali consumed in titrating from colorlessness to 
a full pink, has been found to diminish as the strength of the acid (as indicated 
by its ‘‘affinity constant’’) increases. The limits vary from a fraction of a drop 
to several cubic centimeters. Presence of carbonate in the alkali, or of carbon 
dioxide in the water, increases the transition interval, and is very detrimental to 
sharpness whenever the impurity is at all considerable. A decinormal alkali 
prepared from the purest commercial caustie soda and ordinary distilled water 
will, however, be found sufficiently pure for practical use. A blank titration of 
two or three drops of acetic acid will quickly determine the condition of any doubtful 
alkali solution. Within quite wide limits, the abruptness of the color change in an 
end reaction is independent of the quantity of substance dissolved. An acid 


GENUS III. ACIDS. 37 


containing an appreciable quantity of a phenol as an impurity will titrate like a 
phenol, the pink color appearing gradually after the acid has been neutralized. 
Aromatic oxyacids (e.g. salicylic acid) titrate as sharply as other acids of the 
same strength that do not contain phenolic hydroxyl. Polybasic acids with 
several carboxyl groups also titrate sharply, the end reaction first appearing when 
‘all the carboxylic hydrogens have been replaced. 

Although a small bottle of approximately decinormal alkali, and a glass tube 
medicine-dropper with a rubber nipple, are all the apparatus that is absolutely 
necessary for the performance of Test III as a generic reaction, it is strongly recom- 
mended that the alkali should be carefully standardized, and used from a burette 
mounted in the manner to be described in Test 301. Accurate neutralization 
equivalents of an unknown acid may then be quickly determined while making 
the generic test, without involving any additional manipulations, and will be found 
nearly or quite as useful as melting-point or boiling-point data in completing the 
identification. 

The time limit stated in the direction to ‘‘ Titrate to a pink color that does 
not disappear after stirring for one minute,” is imposed for several reasons. The 
first of these is, that nearly insoluble acids, towards the end of a titration when 
the quantity in suspension has become small, neutralize the dilute alkali very 
slowly. Yet, if the stirring were to be continued for a much longer period, the 
color would eventually fade away through absorption of carbonic acid from the 
air; or, in the case of many esters, from the gradual neutralization of alkali by 
saponification. A few esters like methyl formate, dimethyl oxalate, and some 
esters of hydroxyacids, do neutralize decinormal alkali within the time limit selected, 
and are, in consequence, described with the acids; but this behavior is very excep- 
tional, as has been found by a large number of ester titrations. Isolated cases 
may, however, occur in the tables, in which esters or lactones that should have 
been placed in this genus have been wrongly assigned other positions through this 
cause. 

In titrating acid anhydrides a very characteristic, and at first sight surprising 
phenomenon, will often be noticed. The solution, instead of becoming pink when 
the neutral point is passed and alkali is present in excess, remains colorless; but 
after standing for some time gradually becomes pink. The explanation seems 
to be that the anhydride attacks the hydroxyl groups of the indicator, as in the 
Schotten-Baumann Reaction, so that the power to form colored alkali salts 
is lost. The colorless reaction product is, however, gradually saponified by the 
excess of alkali present after the titration, and the colored salt of the indicator is 
again formed. Confirmation of this explanation is found in the fact that direct 
titrations of acid anhydrides may be successfully made by testing the neutrality 
of the solution from time to time with fresh pieces of phenolphthalein paper. The 
indicator under these conditions is always present in the free state, and so performs 
its proper function. 


General Physical and Chemical Characteristics of the Acids.—The odors 
of the liquid acids vary greatly. The sharp penetrating quality, so familiar in the 
odor of acetic acid, is perhaps the most characteristic element that can be traced in any 
considerable number of species; but even this property is not common to all species. 


38 GENUS III, ACIDS. 


The solid acids are in a majority of cases odorless or nearly so, though there are many ex- 
ceptions to the rule. A sour taste and the power to redden blue litmus are properties 
common to all acids that are sensibly soluble in water. The power of acids, when dis- 
solved in water or alcohol, to instantly and completely neutralize alkalies, is their most 
striking chemical characteristic, and has been discussed in the preceding paragraphs. 


The melting-points, boiling-points, and neutralization equivalents of the tables 
always have reference to the dry acids when these can be obtained jree from water of 
crystallization by drying in an oven at 100°-110°. For a few species which can 
not be easily freed from water of crystallization, the data relate to the air-dried 
acid. In these exceptional cases the hydrated condition of the acid is always made 
evident in the tables by the context. The number of acid species that occur com- 
bined with water of crystallization which may be expelled below 110° is large. 

Genus III has a Division A of solid, and a Division B of liquid, species. Of 
these divisions A is much the larger. Each division comprises two sections, 
1 and 2, of which 1 contains “‘soluble acids,’’ i.e. such as are soluble in less than 
fifty parts of cold water, and 2 the ‘“‘difficultly soluble acids.’’ Where serious 
doubts have arisen as to the sectional position of an acid it has been mentioned in 
two sections. The solubilities of the acids have, however, been more carefully 
studied than those of any other equally important group of compounds. 

To find the section in which an unknown acid is to be sought, it is always 
necessary to at least roughly determine its solubility. This may be rapidly accom- 
plished as follows: 

Weigh out 0.2 grm. of the acid—in the form of an impalpable powder, if it is a 
solid, in a five-inch test-tube. Add cold water in small measured portions from 
a graduate or pipette, shaking thoroughly and persistently after each addi- 
tion. If complete solution is effected by 1 cc., the substance will be described * 
as ‘‘very soluble,” or ‘“‘v. s.”; if by 1-4 cc., as “ easily Soluble” Gre eee 
if by 4-10 cc., as “soluble,” or ‘“s.”; if by more than 10 cc., but less than 
about 30 cc., as ‘‘difficultly soluble,” or ‘“d. s.’”’ Greater degrees of insolu- 
bility are expressed by the terms ‘‘ very difficultly soluble,” or ‘‘ vy. d. s.,” and “ in- 
soluble,’ or “i.” If the supply of the acid is very limited, it is possible to make the 
solubility determination in a smaller test-tube, using only half the quantities of 
substance and solvent that have been recommended. 


* It is impossible to be entirely consistent in the use of this approximate solubility ter- 
minology, because many of the solubility data incorporated in the tables are merely literal 
quotations from authorities who have given no numerical values, and who have probably attached 
a different and less definite meaning to the terms of this solubility scale. 


COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I}. 


GENUS III, ACIDS. 


DIVISION A, SECTION 1,—SOLID ACIDS “SOLUBLE” IN COLD 


WATER. 





Melting-point 
(Oley 





15 
15-5 
17 


18 


27 
29-30 
31 


32-3 


33 


35°5 
40-2 


Neut. 
Equiv. 


86 
86 
86 


90 


112 
158 


118 


130 


116 


102 
144 
104 
166 
100 


100 
156 





SOLID ACIDS.—Colorless and generally Soluble (see note, p. 38) in 


50 parts of cold water. 


Methacrylic Ac.—Cf. Div. B, Sec. 1, b. p. 162°-3°. 

t Isocrotonic Ac.—Odor like butyric ac._—Cf. Div. B, Sec. 1, b. p. 169°. 

Trimethylenecarbonic Ac., C,H,;.CO,H. — B. p. 182°-2-5°. G, 

_ 1-0879?°/,.— ‘Somewhat”’ s. aq. 

{ i-Lactic Ac., Me.CHOH.CO,H.—B. p. (12 mm.) 119°.—Ordinarily 
a hygroscopic syrup containing some anhydride, and hence giv- 
ing too high a neut. eq.— Misc. w. aq., alc., or eth.— Heated in test- 
tube decomposes, gives off white vapors and leaves a viscous 
residue. Gives a-hydroxyacid Test 302 /—Warm sol. quickly decol- 
orizes neutral permanganate w. effervescence.—} Heat nearly to 
dryness 1 cc. lactic acid in a large test-tube over a moderate 
flame, using an inverted closed capillary to prevent bumping. 
Conduct the vapors through a glass tube abt. 25 cm. long into 
2 cc. aq. in a test-tube surrounded by cold water. Test this sol. 
(no odor of acetaldehyde) by Test 111 for acetaldehyde.— 
Neutral salts all s. aq.—{d. and 1. lactic acids are likewise soluble 
acids giving the same reactions]. 

Propylacetylenecarbonic Ac., Pr.C:C.CO,H.—Violet color w. FeCl, 
—AgA ppt. 

Octanon(7)-oic Ac., Me.CO.C;H,,.CO,H.—Tbl. e. s. aq.—AgA, tbl. 
e. s. h. aq. 

a-Oxyvalerianic Ac., Me.(CH,),.CHOH.CO,H.—Hygroscop. ndl.; v. 
s. aq., ale., or eth. Gives Test 302! Gives anhydride easily.— 
AgA, scales, d. s.c. aq.; CaA,, ndl., s. in 28 pt. aq. at 15°; ZnA,+ 
2 aq. s., in 136 pt. aq. at 15°. : 

G-Propionylpropionic Ac., Et.CO.(CH,),.CO,H.—V. s. aq., alc., or eth. 
Violet color w. FeCl,—AgA ppt. 


{ Levuiinic Ac., Me.CO.(CH,),.CO,H.—B. p. 245°-6°.—Deliquescent ; 


usually met with in liq. state. E. s.aq., ale., or eth. Easily 
oxid. by CrO, mixture—Gives iodoform by Test 801 immediately 
_in the cold. In CHCl, sol. 4Br gives stable C;H,Br,03, which 
cryst. fr. aq. w. m. p. 114°-15°.—Ca and Ba saltse.s.aq.; AgA 
characteristic lfts., s. in 150 pt. aq. at 17°. 
Trimethylacetic Ac., Me,.C.CO,H.—B. p. 163-7° (th. i.).—S. in 45 pt. 
aq.—Ag, Zn, and Pb salts all ppts. fr. moderately conc. sols, 
w-Acetylvalerianic Ac., Me.CO.(CH,),CO,H.—B. p. 250°-53° at 280 
mm.—Cryst. e. s. aq., alc., oreth. AgA ppt. lft. fr. h. aq. 

+ a-Oxybutyric Ac., Me.CH,.CHOH.CO,H.—B. p. 255°-60° d. Salts 
generally deliq. and v. s.—Gives a-hydroxyacid Test 302! 

o-Oxyphenylglycollic Ac., HO.C,H,.CO.CO,H.—Nadl. fr. bz.; s. aq. (2); 
e. s. alc. or eth.—Dist. gives CO, and salicylic ac. (Test 319). 

a-Ethylacrylic Ac., CH,: CEt.CO,H.—B, p. 180°.—AgA, lft., s. h- 
aq.—Unsaturated (Test 304). 

Angelic Ac.—Cf. Div. A, Sec. 2.—B. p. 185° (th. @.). 

Diallyloxalic Ac.—Cf. Div. A, Sec. 2. 





39 


40 GENUS III, DIV. A, SECT. 1. 


(ORDER I, SUBORDER I.) 








Moelting-point Neut, |SOLID ACIDS.—Colorless and generally Soluble (see note, p. 38) in 

Choy Equiv. 50 parts of cold water. 

54 118 | + Dimethyl Oxalate, C,0,Me,.—B. p. 163-3° (cor.). Monoclin. tbl. 
Titrates like a monobasic ac.—Add several vols. strong NH,OH 
to conc. aq. sol.; a heavy cryst. ppt. of i. oxamide immediately 
forms. 

55-6 192 | d-Phenyllevulinic Ac., Ph.CH,.CO.C,H,.CO,H.—Silky ndl.; s. aq.; 
e. s. alc.—BaA,+14 aq. e.s. aq.; AgA curdy ppt., lifts. fr. h. aq. 

57-8 130 | Paraconic Ac., C,H,0,.CO,H.—Deliq. mass. Heated gives citraconic 
anhydride. 

60-2 132 | a-Oxycaproic Ac., Me.(CH,),,CHOH.CO,H.—Gives Test 302. On 


long heating at 100° partly sbl. and is slowly changed to a syrupy 
anhydride i. aqg.—Warmed w. CrO, mixture gives valerianic alde- 
hyde and acid (odor). 

64-5 100 | + Tiglic Ac., Me.CH:CMe.CO,H.—Pr or tbl. rather d.s.c¢. aq.; e.s. 
h. aq.—B. p. 198-5° (th. i.)—Peculiar sharp ‘‘spicy’”’ odor.— 
Gives Test 304 (w. KMn0O, instantly—w. Br, only upon heat- 
ing).—CaA,+3 aq., s. c. aq. and, unlike the angelate, more s. h. 
than c.; mod.s. ale. (unlike angelate).—AgaA cryst. scales fr. h. aq. 


64-5 144 | 2-Methylhexanol(4)-oic(6) Ac., C;H,,0;.—Lustrous Ift., e. s. ¢. aq. 
or eth.— Aga scales, e. s. h. aq. 
65-6 150 | Benzoylformic Ac., Ph.cO.CO,H.—Heated gives benzoic ac. (Test 


312), CO,, and benzaldehyde (odor).—V. s. aq.—Ba, Pb, and Ag 
salts d. s. ppts. The acid ppts. oily fr. salts and solidifies on 
standing in desiccator. It gives the ketone reactions. Warmed 
w. conc. H,SO,, it gives benzoic Ac. and CO,.—Cf. Ber. 12, 1505, 
for additional specific reactions. 


66-8 118 | a-Methyl-a-oxybutyric Ac., Et.CH(MeOH).CO,H.—Cryst. sbl. at 90° 
in ndl. V. s. aq., ale., or eth. Gives Test 302.—BaA, v e.s. 
aq.; AgA s. aq. 

69-5-70 50 | @-Dimethylacrylic Ac., Me,.C:CH.CO,H.—B. p. 195°.—Sbl. in ndl. 
—PbA,+ H,0 Ift., e. s. aq.—Unsaturated. 
70 114 | 2, 3-Dimethyl-buten(2)-oic(1) Ac., C,H,,0O,.—Ndl. fr. aq.; 100 pt. aq. 


dissolve 5.15 pt. at 19°-—BaA,+34 aq., powder, e. s. aq. Turns 
yellow in air. Unsat. 
72 43 | + a-Crotonic Ac., HCMe:HC.CO,H.—B. p. 185° e.—S. in 12 pt. aq. 
at 15°.—Ba and Ca salts e. s. aq.; AgA curdy ppt.—Reduction 
of boiling aq. sol. by Na amalgam gives butyric ac. easily.—Gives 
Test 304! 
73 132 | [—], 2-Methyl-pentanol(4)-oic(5) Ac., C,H,,0,—Ndl. sbl. at 100°. 
At 225° gives svrupy anhydride.—V. s, aq., ale., or eth.—Zn salt, 
scales, s. in 300 pt. aq. at 16°, or 204 pt. at 100°.—Gives Test 302. 
74 144 | Mesitonic Ac., Me,.C(CO,H).CH,.CO.Me.—Small pr. fr. aq.—S. aq.; 
v. s. ale. or eth.—Dist. gives an anhydride w. m. p. 24° and b. p. 
167°.— Salts vs s. aq. 





74-5 138 ap-Dioxybutyric Ac., C,H,0,+aq.—Long deliq. pr.; v. s. aq. and 
alc.; i. eth. Effloresces over H,SO,. Gives Test 302. 
74-5 120 | $-Methylisoglyceric Ac., Me.(CHOH),.CO,H.—Pr.; e s. aq. or alc.; 


d.s.eth. Cryst. w. 1 aq. Effloresces over H,SO,.—AgA, fr. h. 
aq., v. stable —Gives Test 302. 
74-6 87 | (8)-s-Dimethyladipic Ac., CO,H.CHMe.(CH,),.CHMe.CO,H.—B. 

321°.—E. s, c. aq., alc., oreth. Heated w. dil. HCl at 200° gives 
a acid w. m. p. 140°. 

76 84 | Tetrolic Ac., MeC: C.CO,H.—B. p. 203°.—Broad tbl., s. aq., eth., or 
CS,. Sbl.—Gives Test 304. Dec. at 202° to CO, and allylene.— 
Salts all s. and reduce Au and Hg sols.—Heat w. conc. aq. KOH 
sol. at 105°, Distil, and test for acetone in the distillate 
(Test 711). 

76 80 | Sec.-Butylmalonic Ac., Bu.CH.(CO,H),.—Cryst. fr. bz. E. s. aq., 
alc., or eth.—Gives Test 303.—AgA ppt. 


ee EN eee 


Melting-point 
(C.°). 
77-8 


76-80 
78-9 


79 after Sbl. 


at 50° 


80 


80 


82 


82-3 


84 


83-6 


87-8 -5 


89 


90 





Neut. 
Equiv. 





73 
81 


76 


104 


132 


87 


166 


166 


166 


108 


GENUS III, DIV. A, SECT. 1. 41 


(ORDER I, SUBORDER I.) 





SOLID ACIDS.—Colorless and generally Soluble (see note, p- 38) in 
50 parts of cold water. 


a-Methylglutaric Ac., CO,H.CHMe.(CH,),.CO,H.—Pr. v. s. aq,, alc., 


oreth. Boiled 20 min. gives oily anhydride, b. p. 272°-75°. 

[+ or —j Ethoxysuccinic Ac., CO,.H.CH,.CHOEt.CO,H.—Pr. v. s. aq. 
Opt. active.—CaA (100°) v. s. c. aq. 

1 Glycollic Ac., CH,OH.CO,H.—Lft. fr. eth.; deliq. if not absolutely 
pure. S. aq. and not easily extracted by eth.—Long heating at 
100° gives anhydride, C,H,O,, m. p. 128°-30°, i. eth., alc., and c. 
aq.—Gives Test 302! Solubilities of salts in water:—BaA,, 
1:79; CaA,, 1: 82 at 10° (easily supersaturates); PbA,, 1 : 32 
at 15°; CuA,, 1: 184; AgA+14 aq., e. s. c. aq., e. dec. by h. ag. 

a-Oxyisobutyric (Acetonic) Ac., Me,.COH.CO,H.—Hygroscopic pr, v. 
s. aq., alc., or eth. Gives Test 302.—CaA, v. s. aq.; AgA scalex 
s. in 14 pt. c. aq.— Fusion w. KOH gives acetone (Test 711). 

+ Citraconic Ac., Me.C(CO,H):HC.CO,H.—Dist. gives anhydride, 
b. p. 213°-4°. Deliq. 4-sided pr. s. in 0.42 aq. at 15°. Aq. sol. 
boiled w. HCl gives mesaconic acid, which is also formed on 
evaporating sol. containing mineral acids.—(NH,),A, boiled w. 
FeCl, sol. (avoid excess), gives red ppt.—Ba salt, tbl. v. d.s. c. aq.: 
PbA, ppt. fr. h. sol.; Ag,A ndl. fr. h. aq.—Unsat., but gives Test 
901 only w. boiling aq. Br sol. 

Oxydiethylacetic Ac., Et,.COH.CO,H.—Triclin. cryst. Sbl. fr. 50° 
V. s. aq., alc., or eth. BaA, v. s. aq., alc., or eth. ZnA,, scales 
s. in 301 pts. aq. at 16°, less s. hot —Gives Test 302. 

Pentylmalonic Ac., C,H,,.CH.(CO,H),—Clear pr. Dec. at 140° giv- 
ing CO, and cnanthic ac. (Test 303).—V. s. aq., alc., or eth. 

o-Hydrocumaric Ac. (Melilotic Ac.), HO.C,H,.(CH,),.CO,H.—(In 
Melilotus officinalis). Dist. gives anhydride.—S. in 20 pt. aq. at 
20°; e. s. ale., eth., and h. aq.—FeCl, gives transient bluish color 
in aq. sol.—Fusion w. KOH gives acetic and salicylic ac. (Test 
319).—CaA, v. d. s. c. aq.; BaA,+3 ag. e. s.; PbA, cryst. ppt.; 
AgA curdy ppt. (ndl. fr. h. aq.). 

m-Methylmandelic Ac., Me.C,H,.CHOH.CO,H.—Lust. pr. fr. bz.; e. 
s. aq., alc., oreth. Gives Test 302. 

a-Oxyisovalerianic Ac., Me,.CH.CH,OH.CO,H.—Rhomb. tbl. volatile 
at 100°. V. ss. aq., ale., or eth.—Oxid. by CrO, mixture.—Dil. 
H,SO, at 130°-40° gives formic ac. (Test 315) and isobutyric alde- 
hyde.—Ca, Zn, and Ag salts d. s. c. aq. 

2, 2-Dimethylpentanedioic-(1, 5)Ac., C,H,,0,.— Woolly, ndl. fr. cone- 
HCl, e. s. aq.—M. p. of anhydride 38°; b. p. abt. 265°. 

3-Methylpentanedioic(1, 5) Ac., Me.CH.(CH,.CO,H),.—Glassy cryst. 
e.s.aq., alc.,oreth. Distil. gives anhydride, m. p. 46°; b. p. 283°. 
—CaA (at 150°) s. aq.; Ag,A ppt. i. aq. 

i-Ethoxylsuccinic Ac., CO,H.CH,CHOEt.CO,H.—V. s. aq., alc., or 
eth.—CaA Vv. s. aq. 

Isopropylmalonic Ac., Me,.CH.CH.(CO,H),.—Dist. gives CO, and iso- | 
propylacetic ac. (Test 303).—E. s. alc. or eth.—Cryst. fr. bz. w. 
2C,H, in long ndl. which effloresce.—Ag,A cryst. powder, i. aq. 

trans.-Pentamethylenedicarbonic(1, 3) Ac., C,H,.(CO,H),.—Flat. pr. 
fr. CCl,, s.in 1 pt. c. aq.— Ag, Vv. d. 8. aq., stable. 

Tigliceric Ac., C,H,(OH),.CO,H.—TDbl. fr. eth.; v. s. aq.; i. CHC];.— 
CaA,, (at 100°), hard white mass, v. s. aq.; s. abs. alc. 

[—]}Arabonic Ac., HO.CH,.(CHOH),.CO,H.—Evaporation of aq, sol. 
gives syrupy anhydride solidifying in dessicator (m. p. 95°-8°— 
BaA, ppt’d cryst. fr. aq. sol. by ale—Gives Test 302. 

Methoxylphenylglyoxylic Ac., MeO.C,H,.CO.CO,H.—WNd1l. fr. bz. v. s. 
alc. or eth. 

n-Heptylsuccinic Ac., C,,H,,0,—Scales, e. s. aq. or CHCl;—Ag,A i. 
aq.; CaA+ aq., d. s. white powder. 





42 


ewes 9 ne 


Melting-point 
CO2)s 


90 


90 


91 


90-1 


92 


93 


93 


93-4-5 


95 


95 


95 
96 


96 


97-5 


95-100d. 


97-8 


98d. 


98 


99 


100 


100 





GENUS III, DIV. A, SECT. 1, 


(ORDER I, SUBORDER I.) 


Neut. [SOLID ACIDS.—Colorless and generally Soluble (see note, p. 38) in 


Equiv. 


178 


80 


193 


160 


166 


87 


80 


180 


74 


19 
152 


73 


68-5 


04:5 


166 


87 


73 


63 


70 


80 


50 parts of cold water. 





Monoethyl Tartrate, CO,Et.(CHOH),.CO,H.—Deliq. rhombic pr. s. 


in aq.—PbaA, lft. d. s. c. aq.; BaA,+2 aq. s. c. aq.—Gives Test 
302.—Saponification gives tartaric acid. 

Terpenylic Ac., C,H,.0,.—Cryst. w. 1 aq. (m. p. 57°).—(An oxidation 
product of oil of turpentine.)—Cryst. s. aq. or eth.—Sbl. at 130°- 
40°. Heat dec. to CO,, etc.—CrO, easily oxid. to acetic acid 
(cf. Tests 702 and 311), CO,, etc., but may be evaporated w. HNO, 
(sp. gr. 1-30) without change.—Monobasic to carbonates; dibasic 
to hot alkalies—BaA d.s. h. aq.; BaA, v. e. s. aq. 

Propylsuccinic Ac., CO,H.CH,.CHPr.CO,H.—Cryst. fr. aq. 2:83 pt. s. 
in 100 pt. c. CHCl. 

Atrolactic Ac., (Me)(Ph)(OH).C.CO,H+ 13H,O.—WNadl. or pr. e. s. ¢. 
aq.—Ba salt d. s., and Zn salt v. d. s. in c. aq.—Boiled w. conc. 
HCl gives atropic ac.—Boiling BaO,H, has no action. 

2, 2, 4-Trimethyl-pentanol(3)-oic(1) Ac., C,H,,O;—Cryst. s. in 50 pt. 
c. aq.—Ba and Ca salts e. s. aq. 

Phenyl-(-lactic Ac., Ph.CHOH.CH,.CO,H.—Pr. v. s. c. aq.—At 180°, 
or by boiling w. BaO,H, or dil. H,SO, gives cinnamic ac, (Test 
313).—BaA,, ZnA,, 14 aq. and AgA, d. s. c. aq. 

Isoamylmalonic Ac., C;H,,.CH.(CO,H),.—Silky ndl. fr. bz.—E. s, aq., 
alc., or eth. Loses CO, on fusion (Test 303).—CaA and Ag,A. 
amorph. ppts. 

[+ }@-Methyladipic Ac., C,H,,.(CO,H),.—B. p. 210°-2° (15 mm.). V. 
s. alc.; e. s. lgr—aAg,A ppt. 

Methyl-f-phenyllactic Ac., Ph.CHOH.CHMe.CO,H.—V. s. alc., eth., 
or warm aq.—At 280° gives CO, and allylbenzene.—AgaA cryst. 
ppt. 

-Oxyglutaric Ac., CO,H.CH,.CHOH.CH,.CO,H.—Nad1l. e. s. aq. or alc. 
—Boiled w. 60% H,SO, gives glutaric acid. 

d-Citramalic Ac., C,H,O;.—-Very deliq. cryst. mass. Gives Test 302. 

Phenoxyacetic Ac., PhO.CH,.CO,H.—B. p. 285° w. sl. dec.—Silky 
ndl. e. s. aq., alc., or eth.—FeCl, gives yellow ppt.—Cryst. ppt. w. 
Br aq.—BaA,+3 aq., s. aq.; AgA, d. s. ndl. 

Propylmalonic Ac., Pr.CH.(CO,H),.—Tbl. fr. bz. which contain n 
bz. of cryst. (dif. fr. isopropyl comp.).—Gives Test 303. ' 

+ Glutaric Ac., CO,H.(CH,),.CO,H.—Monoclinic pr.; 100 cc. aq. sol. 
contain 42-9 grms. at 0°; v. s.ale.oreth. Boils w. little dec. at 
302°-4°.—CaA. 4 aq. and BaA. 5 aq., v. 8s. aq.; PbA cryst. ppt.; 
Ag,A ndl. s. h. aq.—Apply Test 316! 

cis-1, 2, 3-trans-1-Trimethylenetetracarbonic Ac., C;H,O,.—H. s. aq., 
alc., or eth. Gives Test 303. 

Phenyl-a-lactic Ac., Ph.CH,.CHOH.CO,H.—Thick pr. fr. aq.—BaaA, e. 
s.aq. Gives Test 302. Heated above 140° gives formic acid and 
a-toluic aldehyde. 

Isoamylmalonic Ac., C,H,,.CH.(CO,H),.—Silky ndl. (fr. bz.+Igr.); 
v.s.c,aq. Gives Test 303: CaA amorph. ppt. 

Ethylsuccinic Ac., CO,H.CHEt.CH,.CO,H.—Pr. v. s. aq., alc., eth., or 
CHCl. Dist. gives liquid anhydride b. p. 243°.—Ba and Zn 
salts e. s. aq. 

+ Oxalic Ac. (Cryst.), (CO,H),+2H,0.—Monoclinie pr. After fusion 
subl. at 150°-60°. S. in 10.46 pt. aq. at 14-5°; e.s. c. ale.; s. in 
79 pt. abs. eth. at 15°; v. d. s. CHCl,;—Apply Test 317! 

+ Citric Ac. (Cryst.), CO,H.CH,.C(OH)(CO,H).CH,.CO,H + H,O.—Cf. 
Citric Ac. m. p. 153°. Gives Test 302! Apply Test 314! 

3, 3-Dimethylpentanedioic(1, 5) Ac., C;H,,0,—Pearly ndl. fr. bz.; 
e. s. aq., eth., or h. bz.—Dist. or action of acetyl chloride gives 
anhydride, m. p. 124°-5°. 





Melting-point 
Ci2y, 


100 


100 


100-1 


101-2 


101-5 


102-3 


103 
103-4 
103-4 

105 


106-7 
107 
107 

110-1 
i 


111 
111-5 


112 
113-5 


113-5 


112-15 





120 


72 


80 


80 


98 


72 


132 


80 


80 


80 
80 
87 
134 
144 


166 
66 


66 


72 


200 


192 


GENUS III, DIV. A, SECT. 1. 43 


(ORDER I, SUBORDER I.) 


SOLID ACIDS.—Colorless and generally soluble (see note, p. 38) in 


50 parts of cold water. 


+[+ or —]Malic Ac., CO,H.CH,.CHOH.CO,H.—Deliq. ndl.; cryst. w. 


difficulty. V.s.aq.; s.ale.oreth. Gives Test 302! Gives with 
PbAc, a voluminous white ppt. which melts to resinous mass on 
boiling w. a little aq.—Salts give no ppt. w. BaCl,, White ppt. 
w. AgNO,. At 175°-200° gives fumaric and maleic acids and 
maleic arihydride.—Apply color test 314! 

2-Methyl-2, 3-propanedioic(1) Ac. , C,H,0,.—_Slowly cryst. syrup; e 
s. aq.; d.s. eth.—CaA, s. aq. 

Ethylmaleic Ac., CO,H.EtC:CH.CO,H.—Thick pr. e. s. aq. or eth.— 
Unsat. (Test 304). Heated gives a liquid anhydride. Na amal- 
gam reduces to ethylsuccinic acid. 

s-Methylethylsuccinic Ac. (fumaroid), CO,H.CHMe.CHEt.CO,H.— 
Ndl. fr. aq.; e.s.c.aq. Heating gives liquid anhydride, b. p. 245°. 

Butylmalonic Ac. Me.(CH,),.CH.(CO,H),.—Pr. e. s. aq., alc., or eth. 
Gives Test 303. At 150° gives CO, and caproic acid (disagree- 
able odor). 

Pentinoic Ac., C,H,.CO,H.—Monoclinic tbl. fr.eth.; ndl.fr.bz. V.s. 
aq.—BaA,, scales fr. dil. ale.; v. s. aq—Unsat. (Test 304). 

Allylmalonic Ac., C,H,.CH.(CO,H),.—E. s. aq. or eth. Adds Br,.— 
CaA, d. s. aq. ; Bad -taq. pearly Ifts. s. in 1 pt. h. aq.; Ag,A, i. 
aq. — Gives Tests 303 and 304. 

a-Hydroxylevulinic Ac., Me.CO.CH,.CHOH.CO,H.—FE. s. aq.; d. s. 
eth. Reduces Fehling’s sol. At 100° gives an anhydride (ndl. 
mop. 203° d.): 

3-Methyl-3-carboxyl-pentanoic (1) Ac., C,H,,0,—Clear pr. fr. aq.; 
e. s. aq., alc., or eth. 100 pt. aq. at 15° dissolve 15-4 pt. acid. 
Heating at 200° gives an anhyd., b. p. 239°-45°. 

Na ie Ac., (CO,H).(CH,) ,,CO,H.—Tbl. fr. aq. s. in 24 pt. aq. at 
20°; e. s. eth.—Sbl. without dec.—BaCl, gives no ppt.; Aga cryst. 
ppt.; “Cad separates as gran. floc. ppt. when saturated sol. is boiled. 

Methylpropylmalonic Ac., (Me)(Pr).C.(CO,H),.—E. s. aq., eth., or 
CHCIl,.—Gives Test 303. 

Isobutyl Malonic Ac., Me,.CH.CH,.CH.(CO,H),.—E. s. aq. or eth._— 
CaA and Ag,A, i. ppts.—Gives Test 303. 


Isobutylsuccinic Ac., C,H,.C,H,.(CO,H),.—Cryst. e. s. aq. or eth_— 


CaAe.s.; BaAd.s. “The anhydride i is liquid. 


Angliceric Ac., C,H,.(OH),.CO,H.—Nadl. fr. eth. V.s. aq.; i. CHCl. 
—Ca salt amorphous, Vv. 8. aq.; 1. abs. ale: 


‘Hexahydrosalicylic Ac., o-HO.C,H,,.CO,H. —+sided tbl. or ndl. e. s. 


aq. or eth. 

m-Hydrocumaric Ac., HO.C,H,.(CH,),.CO,H.—‘‘ E. s. usual solvents.” 

Ethylmalonic Ac., Et. CH.(CO,H),.—Cryst. w.1H,O. Pr. v.s. aq. or 
eth.—Gives Test 303, being completely dec. to CO, and butyric 
ac. (odor) at 160° \—Na,A gives no ppt w FeCl, (dif. fr. pyro- 
tartaric ac. below).—CaA less s. h. than c ; BaA+$ aq., fine pr. d. 
s.aq.; ZnA, 24 aq. characteristic 6-sided tbl. s. in 456 pt. aq. 

Pyrotartaric Ac., Me.CH(CO,H).CH,.CO,H.—Triclinic pr. e. s. c. aq. 
oreth. At 200 gives an anhydride. are v e.s.aq.; BaA-2 aq. 
e. S. aq.; Ag,A, ppt., Vd. 5. fn. ag: 

Aaah a Aa as eee oto Et 2) Ac., Me.C,H;.(CO,H),.—Silky 
ndl. fr. bz. S.in 1 pt. c, aq.; e. s. eth. ” Distillation gives valero- 
lactone.—Gives Test 303 at 140°—Stable towards KMnO,.— 
CaA +5 aq., glassy pr., e. s. aq.; Ag,A, floc. ppt. (at 70°). 

Naphthoylformic Ac., C, ,H,.CO.CO,H.—Ndl.,e.s.aq.oreth. Oxid. by, 
KMn0O, to a-naphthoic ac. Seats S.C. aq.; AgA, amorph. ppt, 

Ethylbenzoylacetic Ac., Ph.CO.CHEt.CO,H.—E. s. alc. or eth. Boil- 
ing w. conc. alcoholic potash gives mixture of potassium benzoate. 
and butyrate ! 


GENUS III, DIV. A, SECT. 1. 


(ORDER 1, SUBORDER I.) 


SOLID ACIDS.—Colorless and generally soluble (see note, p. 38) in 





fone ase 
edickencne pee 50 parts of cold water. 
114-5d. 91 Dioxytartaric Ac., CO,H.[C(OH),.],.CO,H.—Cryst. mass fr. eth. V.s. 
aq. Gives Test 303—The aq. sol., when heated, dec. quantita- 
tively to CO, and tartronic ac.!_ Therefore gives theoretical neut. 
eq. only at 0°. Salts unstable. 
115-16 74 | a-Ethyltartronic Ac., Et.COH.(CO,H),.—Cryst. w. 1 aq. in tbl. w. 
m. p. 64°-70°.—Ag,A, mic. pr. fr. h. aq. 
116 136 | Trioxyisobutyric Ac., (CH,OH),.COH.CO,H.—Pr. fr. alc. v. s. aq.; d. 
s. ale. or eth.—Gives Test 302.—CaA,+4 aq., s.aq.; PbA,.Aq., d. 
Sond. 
116-5 164 | Hydrocumarilic Ac., C.H,O.CO,H.—Pearly lft. fr. aq.; s aq.; v.e.s. 


alc. or eth. Dist. w. dec. at abt. 300°.—AgA, v. d. s. h. aq.; 
BaA,+2 aq., e. 8. aq. 

117 80 | Isopropylsuccinic Ac., CO,H.CHPr.CH,.CO,H.—Cryst. crusts e. s. aq., 
alc., eth., or CHCl,.—On distill. gives liq. anhydride, b. p 245°-50°. 
—Fuse w. KOH and acidify w. H,SO,. (Odor of butyric ac.). 
—BaCl, no ppt. Ag salt, d.s. 


sbi leg 97 | Benzylmalonic Ac., Ph.CH,.CH.(CO,H)..—Triclinic, es. aq. or eth, 
Test 303 at 180° gives CO, and hydrocinnamic ac 
117-8 166 | Tropic Ac., Ph.CH(CH.OH).CO,H. (prepared fr. atropine).—Ndl. or 


tbl. s. 49 pt. aq. at 14-5°; v.d.s c. bz and CS, Gives Test 
302.—CaA,-4 aq., rhombic tbl.—Long boiling w. Ba(OH), gives 


atropic ac. 

118 73 | Methylethylmalonic Ac., (Me)(Et)C.(CO,H),.—Pr. e. s. aq. or eth.— 
Ag,A, d. s. eryst. powder.—Gives Test 303. 

118 152 + Mandelic Ac., Ph.CcHOH.CO,H.—Rhombic cryst., 16 pt. s in 100 pt. 


aq. at 20°; s. eth—Gives Test 302 !—Dist. or boiled w aq. and 
MnO, gives odor of bitter almonds!—AgaA cryst. ppt., tbl. fr. h. 
aq.; BaA,, s. 12 pt aq. at 24°. 

119 74 Citramalic Ac. (racemic), CO,H.CH,.C(OH,Me).CO,H.—Glassy deliq. 
cryst. v. s. aq —At 200° gives citraconic anhydride.—Gives Test 
302.—CaCl, added to NH, salt gives floc. ppt. in cone. sol.—Scaly 
fr h. dil. sol. 


119-20 68 | Mesoxalic Ac., (HO)..C.(CO,H),.—Deliq. ndl., vs. aq.; s. eth.—Re- 
duces ammon. AgNO, sol. when warmed.—Ba, Ca, Pb, and Ag 
salts v. d. s. ¢ aq.—Ag,A dec. by boiling w. aq., oxalic ac. being 
among the products. 

120d. 85 | 4’-Tetrahydrophthalic Ac., C,H,,0, (dried i. v.)—Lfts fr. aq.; e. s. 
aq.—Oxid. by alk. KMnO, to adipic ac —At 100° gives anhy- 
dride, m. p. 74°.—BaA+aq,., gran. ppt.—Gives Test 304. 

120-1 94 | 2, 3, 3-ITrimethylpentanediol(2, 4)-dioic(1, 5) Ac. (racemic), C,H,,0,. 
—(An oxid product of camphoric acid.) Lust. lfts.,e s aq., ale., 
or eth.—Heated to 220° dee to water, isobutyric ac. (odor and 
Test 311!), CO, ete —Ag,A ppt. 

123 74 | §-Methylmalic Ac., CO,H.CHMe.CHOH.CO,H.—Pr. fr. acetic eth., v. 
s. aq. or ale —Gives Test 302 —Heat gives citraconic anhy- 
dride, etc —BaA +24 aq. Ift ds. aq. 


123 166 | [—}Tropic Ac., Ph.CH(CH,OH).CO,H.—Cryst. somewhat s. aq.—M. 
p. of quinine salt 178°. 
121-5 80 Diethylmalonic Ac., Et,.C.(CO,H),—Pr, v s. aq. or eth.—Gives 





Test 303 at 170°-80°, forming CO, and diethylacetic acid.—Zn 
salt cryst. ppt.—CaCl, precipitates conc. sol. of NH, salt. 


124 80 | Methylisopropylmalonic Ac., (Me)(Pr).C.(CO,H),—S. aq.—Gives 
Test 303.—CaA, v.d.s aq.: Ag,A ppt. 

127-8 166 | [+] Tropic Ac., Ph.CH(CH,OH)CO,H.—Pr. fr. eth. S.h.aq. M.p. 

of quinine salt 186°-7°. Lesss. dil. ale than salt of [—] tropic ac. 

128 80 | s-Dimethylglutaric. Ac. (malenoid), CO,H.C,H,,.CO,H.—Triclinic 


cryst.—100 pt. aq. at 17° dissolve 4.1 pt.—Acetylchloride gives 
anhydride in the cold, b. p. 272°. 


Melting-point 
(C.°). 


128c. 


129 


129 


129 


129 


129-31 


130 


131 


131 


132 


132 


132 


133 


133 


132-4c. 


135d. 


Neut. 
Equiv. 


90 


87 


152 


73 


166 


81 


58 


194 


72 


73 


52 


65 


57 


92 


112 


59 





GENUSVIUIS DIVs AS SECTS 1: 45 


(ORDER I, SUBORDER I.) 





SOLID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in 


50 parts of cold water. 





[+ or —}Trioxyglutaric Ac., CO,H.(CHOH),;.CO,H.—Cryst. fr. ace- 
tone; v.s. aq. or alc.—Ag,A ppt., m. p. w. dec. 173°.—Gives Test 
302. 


s-Diethylsuccinic Ac., CO,H.EtCH.CHEt.CO,H.—Warty masses; v. e. 
s. h. aq. or eth.—ZnA more s. c. than h.—At 180° gives anhydride. 


m-Oxyphenylacetic Ac., HO.C,H,.CH,.CO,H.—V.s. aq. oreth. Gives 
transient violet color w. FeCl. 


s-Dimethylsuccinic Ac. (malenoid), (MeCH),.(CO,H),.—Pr. s. in 3-3 
pt. aq. at 14°—W. Conc. HCl at 180° gives much of the malenoid 
R641... Dp. 209. 


Phloretic Ac., p-HO.C,H,.CH(Me)(CO,H).—S. c. aq. or eth. Gives 
green color w. FeCl, !—Pb salt bulky ppt. 


$£-Dimethylmalic Ac., CO,H.CHOH.CMe,.CO,H.—Cryst. fr. acetic eth, 
E. s. aq.; s. eth.—Ag,A, ndl.d.s.h.aq. Gives Test 302! 


+-Maleic Ac., CO,H.CH:CH.CO,H.—Monoclinic pr. s. in 2 pt. aq. at 
10°. Gives Test 901 w. h. bromine water, but does not add Br 
easily in CCl, sol.—Heating in vacuo above 100° gives solid anhy- 
dride, m. p. 56°—7°.—At 200° in tube gives fumaric acid (d.s. aq., 
sbl. at 200°).—Aq. sol. gives ppt. w. BaO,H,; PbAc, gives ppt. 
No ppt. w. CaCl,.—t} Place 0-1 grm. acid w. 0-2 cc. aniline in a 
test-tube w. 10 em. glass tube as return condenser. Heat 1 hr. 
at 190°-200°. Cryst. fr. 15 cc. boiling ale. Cool, filter, wash w. 
2 ce. cold ale. and recrystallize fr. 10 cc. boiling ale. Dry at 100°- 
110°. Gives phenylaspartic-anil. white cryst., m. p. 209°-10°. 


Phenyl-(-oxyvalerianic Ac., Ph.C,H,.CHOH.CH,.CO,H.—H. s. aq.; d. 
s. c. eth.—Dec. on dist.—BaA,+aq,., lfts. d.s. aq.; AgA curdy ppt. 


trans-Tetramethylenedicarbonic(1, 2) Ac., C,H,.(CO,H),.— Lust. ndl. 
fr. HCl. Goes easily into anhydride, m. p. 75°. 


s-Methylethylmalic Ac., CO,H.CHEt. (Me)C(OH).CO,H.—Pr. e. s. aq. 
Dec. on dist. Gives Test 302. 


+ Malonic Ac., CH,.(CO,H),.—Cryst. s. in less than 1 pt. aq.; s. eth.— 
Test. 303 gives CO, and acetic ac.!—Fuming nitric acid causes 
evolution of CO,.—tT Boil 1-2 cgrm. in a test-tube w. 3 cc. acetic 
anhydride for 3 minutes; then dilute w. 3 cc. acetic ac. A yel- 
lowish-red sol. w. yellowish-green fluorescence will be obtained.— 
Ag,A stable cryst. ppt.; CaA+2H,0, alm. i. c. aq. 


Glutaconic Ac., CO,H.CH,.HC:HC.CO,H.—Pr. e. s. aq. or eth.— 

_  YZmnA less s. h. than c.—Ag,A d. s. h. aq.—Long boiling w. x’s 
acetyl chloride gives anhydride, m. p. 87°.—Reduction w. Na 
amalgam gives glutaric ac. 


i-Malic Ac., C,H,O,.—Cryst. Not deliq.—Reactions as for [+ ac.] 
bGtar. p.t00e:) 


Diallylmalonic Ac., (C;H,),.C.(CO,H),.—Pr. e. s. aq. or eth. Gives 
Test 303 and 304.—CaA (at 100°) e. s. aq.; Ag,Ad. s. c. aq. 


Pyromucic Ac., C,H,0.CO,H.—Sbl. fr. 100° in ndl.—S. in 28 pt. aq. 
at 15°. V.s. h. aq.; e. s. alc. or eth.—Pine splinter, soaked in 
conc. HCl and held in vapor evolved on heating dry NH, salt in 
test-tube, becomes deep red !—Sol. in conc. H,SO, warmed w. 
trace of isatin becomes violet-blue.—Aq. sol. gives reddish-yellow 
ppt. w. FeCl,.—CaA, and BaA, cryst. and s. aq. or ale.—PbA,+ 
aq. d. s. c. aq.— Aga lft. 

Isosuccinic Ac., Me.CH.(CO,H),.—Pr. v. s. aq.; 100 cc. aq. sol. at 0° 
contains 44.3 grm.—Test 303 gives CO, and propionic ac. (Test 
311) Ca, Ba, Pb, and Ag salts v. d. s.; Pb salt s. in x’s of pre- 
cipitant. 





46 GENUS III, DIV. A, SECT. 1. 


(ORDER I, SUBORDER I.) 





Melting-point Neut. |SOLID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in 
(C.), Equiv. 50 parts of cold water. 








135d. 73(?) | | Acetonedicarbonic Ac., CO.(CH,.CO,H),.—Ndl. fr. acetic eth. which 
effloresce in the air.—V. s. aq. or alc.; d. s. eth.—Aq. sol.+ FeCl, 
gives violet color! Gives Test 303!—-Distil a neutral aqueous 
solution of the sodium salt and apply tests for acetone (Test 
711) to distillate ! 


130-8 72 Cis-1, 2-Tetramethylenedicarbonic Ac., C,H,.(CO,H),.—Feathery cryst. 
v. s. aq., alc. or eth.—Heated above 300° gives anhydride, m. p. 
76°-8°.—Oxid. by KMn0O, to oxalic ac.—BaA separates as 6-sided 
tbl. on boiling a sol. in ammonia w. BaCl, sol. 


137 72 | Methylglutaconic Ac., Me.CH.(CO,H).CH:CH.CO,H.—E. s. aq,, alc., 
or eth.— Unsaturated. 
137 152 o-Oxyphenylacetic Ac., HO.C,H,.CH,.CO,H.—Ndl. fr. eth.; s. aq.— 


Dist. gives anhydride, m. p. 49°; b. p. 236°-8°.—Aq. sol. colored 
violet by FeCl, ! 


138-9 210 Veratrinketonic Ac., (MeO),.C,H,.C,0,H (dried).—E. s. aq., alc., or 
eth.—KOH fusion gives protocatechuic ac.—Pb salt d. s. ppt. 
138-9 72 Cis-Tetramethylenedicarbonic(1, 3) Ac., C,H,.(CO,H),.—Pr. v. s. c- 
aq.—BaA-+2 aq. s. in 150 pt. c. aq., less s. in h. aq. 
139 87 Dimethylethylsuccinic Ac., CO,H.CHEt.CMe,.CO,H.—S. in 27 pt. c. 
aq.; e.s. alc. or eth.—B. p. 235°-40°. 
139 Anhydrocamphoric Ac., C,H,,0;.—Sbl. undec.—H. s. aq., alc., or eth 
Can be recryst. fr. aq. 
139-40 io a-Dimethylsuccinic Ac., CO,H.CMe,.CH,.CO,H.—Thick glassy pr. fr. 


bz.—100 pt. aq. at 14° dissolve 7-52 pt.; e.'s. ale. or eth.—At 
165°-70° gives anhydride, m. p. 29°.—Ca salt separates from 
ammon. sol. by CaCl, only when warmed. 


139 101 Tetrahydroxyterephthalic Ac., (OH),.C,.(CO,H),.—E. s. aq. or ale.; 
i. eth. No color w. FeCl,.—BaaA e. s. aq. 
139 182 | Hydrocaffeic Ac., (OH),.C,H,.(CH,)..CO,H.—6-sided tbl. fr. aq. 


E. s. aq. Aq. sol. gives intense green color w. FeCl,! Reduces 
Fehling’s sol. and AgNO, easily. 


140 74 Ethylenemalonic Ac., C,H,.C.(CO,H),+aq.—Ndl. fr. eth., v. s. aq. or 
eth.; s. CHCl,;.—Gives Test 303 and 304.—(NH,),A+ BaCl, gives 
ppt. almost 1. c. aq. 


140 79 | Cis-Pentamethylenedicarbonic(1, 2) Ac., C,H,.(CO,H),.—Ndl. At 160° 
gives anhydride (tbl. fr. Ac., m. p. 140°). 
abt. 140d. 67 | Isomalic Ac., Me.COH.(CO,H),.—Cryst., e. s. aq., ale., or eth.—Opt. 


i.—At abt. 160° gives Test 303 yielding CO, and lactic acid.— 
BaA+2 aq., d. s. h. aq. 


140- 80 | s-Dimethylglutaric Ac. (fumaroid), C,H,,O,.—Pr.—100 pt. aq. at 17° 
dis. 4.4 pt.—CaA, floc. ppt. 

141d. 63-3 | 2, 3-Dicarboxyl-pentanoic(1) Ac., C;H,,0,.— Cryst. fr. acetone, v. s. 
aq., alc., or eth.—Heated loses CO,.—Ba,gA,, 1. aq. or ale. 

140-3 84 Mesotartaric Ac., (HO),.C,H,.(CO,H),.—(Cryst. w. 1 aq.)—Tbl. s. in 


less than 1 pt. ec. aq—KHA much more s. than acid tartrate or 
racemate.—Does not ppt. CaSO, sol. (dif. fr. racemic ac.). Gives 
Test 302.—Opt. i—For microchemical tests cf. R. 17.69. 


143-4s.d. 182 | Phenylglyceric Ac., Ph.(CHOH),.CO,H.—V. s. aq. or alc.; d.s. abs. 
eth.—Gives Test 302, decomposing at 160° to CO, and a-toluylic 
aldehyde.—CaA,-4 aq. d. s. c. aq. 


145-Gd. 64 | Glutinic Ac., CO,H.C: C CH,.CO,H.—H. s, aq., alc., or eth.; i. bz. 
—Gives Test 303 and 304.—PbA ppt. 





Melting-point 
(ORS 


145 


147 


148 


148 


abt. 150d. 


150-3 


151 


GENUS III, DIV. A, SECT. 1. 47 


(ORDER I, SUBORDER I.) 





Neut. [SOLID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in 


Equiv. 4- 


226 


168 


152 


81 


90 


64 


50 parts of cold water. 


Galactosecarbonic Ac., HO.CH,.(CHOH) ,.CO,H.—Nadl., s. aq.—Fusion 
gives an anhydride.—Gives Test 302. 


Homogentisic Ac., (HO),.C,H,.CH,.CO,H.—V. s. aq., ale., or eth._— 
Fusion gives anhydride of m. p. 191°.—Gives transient-blue color 
w. dil. FeCl,—KOH fusion gives hydroquinone, etc.—Cryst. 
effloresce over H,SQ,. 

p-Oxyphenylacetic Ac., HO.C,H,.CH,.CO,H.—Flat ndl.,s. c. aq.; v.e. 
s. h. aq.; s. ale. or eth.—Sol. gives pale-violet color w. FeCl,, 
changing quickly to a dirty grayish green. Dist. w. CaO gives 
CO, and p-cresol. (From urine.) 

Diglycollic Ac., CO,H.CH,.0.CH,.CO,H + Aq.—Rhomb. pr., e. s. aq. 
or ale.—Dist. w. dec. giving glycollic ac., trioxymethylene, CO and 
CO,.—BaA, i: aq.; Ag,A, gray ppt.; CuA blue ppt. 

I-Camphoronic Ac., C,H,,0,.—Cryst. s. in 17 pt. c. aq.; v.s.ale.; e.s. 
eth.—CO, and isobutyric ac. are among products of slow dist. 
cis-1, 2, 3-Trimethylenetricarbonic Ac., C,H,.(CO,H), (dried at 120°). 

—E. s. aq. or ale.—Ca salt less s. h. than c.; Ag,A amorphous ppt. 
a-Oxyadipic Ac., CO,H.C,H,.CHOH.CO,H.—Sbl. undec. E. s. aq. 
alc.; or eth. 

Trimethylsuccinic Ac., CO,H.CMe,CHMe.CO,H.—E. s. aq. or bz.— 
ZnA, mic. pr. e. s. c. aq., but ppt’d by boiling the sol.—Prepare 
the anilic ac., m. p. 134°, and the anil. m. p. 129°. 

i-Trioxyglutaric Ac., CO.H.(CHOH),.CO,H.—Thbl. fr. acetone. 
aq. orh. ale. Gives Tests 101 and 302. 

Hexamethylenetricarbonic (1, 4, 4) Ac., C)H,,0,.—S. aq.; d.s. eth.— 
Dec. at 200°. Gives Test 303. 

Phenylmalonic Ac., Ph.CH.(CO,H),.—Pr., e. s. aq., ale., or eth.—CaA 
eryst. ppt.; Ag,A curdy ppt.—Fusion gives CO, and phenylacetic 
ac. (Test 303). 

+ Citric Ac., CO,H.CH,.C(OH)(CO,H).CH,.CO,H.—Cryst. w. 1 aq. in 
rhombic pr. (Dry at 130° form. p.) S. in 0-75 pt. c. aq.; v.s. 
alc.: 100 pt. c. eth. dissolve 2-26 pt.—Gives Test 302.—Hot conc. 
H,SO, gives yellow color, but does not char.—CaCl, gives a white 
eryst. ppt. with neutral alkali citrates when the sol. is boiled for a 
few min.,—otherwise only after some hours; an alkali citrate 
sol. after being made strongly alkaline w. NaOH gives an 
amorphous ppt. immediately.—Ca,A, is soluble in HCl, in Ac, 
in citric ac., in NH,Cl, and in alkaline citrates—_{Neutral alkali 
tartrates and oxalates give an immediate ppt. w. CaCl,; calcium 
oxalate is insoluble in acetic acid. Malic ac. and neutral malates 
give no ppt. w. CaCl, unless alc. is also added. A cone. sol. of 
citric ac., or of an alkali citrate acidified w. acetic ac., gives no ppt. 
when treated w. a 5% potassium acetate sol. and alc. (dif. fr. 
tartrate) ].—Gives color reac. 314! 

(rac.)-Trioxyglutaric Ac., CO,H.(CHOH),;.CO,H.—Cryst. fr. acetone 
Vos ag. oh. ale: 

1, 1-Tetramethylenedicarbonic Ac., C,H,.(CO,H),.—Pr. fr. eth. E.s. 
aq.; s. eth.—Gives Test 303 at 210°——Ba, Pb, and Ag salts 
are ppts. 

[+ or —] Talomucic Ac., C,H, ,0,.—Mic. lft. fr. acetone; e. s. c. aq. 
or h. ale.—CaA (at 105°), d. s. h. aq. 

Ethenyltricarbonic Ac., (CO,H),.CH.CH,.CO,H.—Pr. e. s. aq., alc., or 
eth. Test 303 gives CO, and succinic ac. (Test 320!). Ca,A, and 
Zn,A, are more s. inc. than in h. aq.; Ag,A is an amorphous ppt. 

Diacetylsuccinic Ac., CO,H.CH(MeCO).CH(MeCO).CO,H.—NadL. s. aq. 
or ale.; d. s. eth.—Heated w. HCl gives carbopyrotritaric ac. 

Tartronic Ac.—See m. p. 185°-7°. 


Vere, 





48 


GENUS lil, DIV. A, SECT: 1. 


(ORDER I, SUBORDER I.) 





Melting-point 
CORE 
161d. 


160-1 
161-6c. 


162d. 
166 
166-7 
166-7 


166-7 


167d. 


167-5 


168-70 


169 


170 
169-71 
172d. 


175 





Neut. 
Equiv. 





65 


132 


fe) 


58-7 


72 
72°7 


ays) 


164 


75 


— 


188 


72 


51-5 


65 


SOLID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in 


50 parts of cold water. 





+ Itaconic Ac., CH,:C(CO,H).CH,.CO,H.—Rhombic octahedra, s. aq. 
(1 <.2°at 207)s sales d: 8. eth.—Gives Test 304. —Gives red- 
brown ppt. on boiling | w. x’s FeCl,.—CaA-aq. s. in 45 pt. aq. ab 
18°; Ag,A v. d. s. h. aq. _"“Warmed w. acetylchloride gives anhy- 
dride, m. p. 68°. 

Saccharine.—Cf. Genus V, Div. A. 

+ Quinic Ac., (OH),.C,H,.CO,H.—Monoclinic pr. s. 2-5 pt. aq. at 9°; 
less s. ale.; alm. i. eth. —Gives Test 302.—Dry distillation gives 
phenol, salicylic ac. (Test 319), and benzoic ac. (Test 312).— 
+ Gives pungent odor of quinone on boiling in test-tube w. dil. 
H,SO, and MnO,!—Br substitutes—I and KOH give iodoform 
(Test 801).—Ca and Pb salts e. s. ¢. aq.—Occurs in cinchona 
bark, coffee-beans, etc. 


Teraconic Ac., Me,.C:C(CO,H).CH,.CO,H.—E. s. c. aq., ale., or eth. 
—Dist. gives aq. and an anhyd. w. b. p. 270°-80°.—CaCl, gives 
pulv. ppt. (best on warming). 

Tricarballylic Ac., CO,H.CH.(CH,.CO,H),.—HE. s. aq. or ale.; d.s. eth- 
—Sbl. w. dec Cd ein d. s. aq.; Pb,A, pulv. ppt.—FeCls 
gives floc. ppt. 

Acetoxyl-a-propionic Ac., Me.CH(C,H,0,).CO,H.—Ndl. v. s. aq. or 
ale. After long keeping becomes i. in ale. and does not melt 
at 300°. Dae v. s. aq.—Boiled w. NaOH gives acetic and 
lactic ac. salts. 

Methylitaconic Ac., Me.CH:C(CO,H).CH,.CO,H.—Pr. s. aq. or eth. 
—Ba salt cryst. ppt.—Gives Test 304. 


Isocamphoronic Ac., C,H,,0,.—Pr. s. c. aq.; e. 8. ale., or eth.— 
Sbl.— Ag, A. —NH, OH and BaCl, give no ppt. 


Dicarboxyglutaric Ac., (CO,H),.CH.CH,.CH.(CO,H),.—V. s. aq., 
alc.; d.s. eth.—Test 303 gives CO, and glutaric ac. (Test 316). 
Ca, Ba, and Pb salts form ppts. 


Prehnitylic Ac., Me,.C,H,.CO,H.—Glassy pr. fr. ale. ‘‘Somewhat”’ 
s. in aq. 

{ d-Tartaric Ac., CO,H.(CHOH),.CO,H.—Monoclinic eryst.—100 pt. 
aq. dissolve 139 pt. at 20°.—HE. s. alc., v. d. s. eth.—Solutions 
[+]. Applv Tests 362 and 314! CaCl, gives volum. ppt. from 
sol. of neutral K or Na salts, but not from solution of the free 
acid. The ppt. is sol. in mineral and acetic acids, in cold N aes 
and in an excess of alkaline tartrate. .From rather dil. sol. 
appears slowly and in ecryst. form. —KC,H,O, gives a ppt. ia 
tartaric acil sols. (facilitated by diluting with an equal vol. of 
alcohol). Neutral salts must first be acidified with acetic ac.! 
—TIf to an aq. sol. of the acid or a soluble tartrate, 1 drop FeSO, 
sol., a few drops H,O, sol. and an x’s NaOH be added, a fine 
deep violet color is immediately produced, which in cone. sols. 
is so deep as to be nearly black. (Cf. Allen, I, 515.) This 
color is not given by citric, malic, succinic, or oxalic acids. 

Naphthol (8)-carbonic Ac., HO. Coie. CO »H.—HE. s. aq., ale., or eth.— 
CaA, sol. gives w. F eC, a violet ppt. 

trans-Tetramethylenedicarbonic(1, 3) Ac., C,H,.(CO,H),..—Sbl. in fine 
ndl.—sS. in 26 pt. aq. at 20°; ‘d.s.eth.—Does not add Br.—Gives 
an anhyd. w. difficulty, m. p. 50°. 

{ s-Ethanetetracarbonic Ac., C,H,.(CO,A),.—E. s. aq., alc., or eth. © 
—Gives Test 303, vielding CO, and succinic ac. (Test 320!). 
Aq. sol. gives ppt. w. BaCl,. 

Oxalacetic Ac., CO,H.CO.CH,.CO,H.—E. s. aq., alc., or eth.—Gives 
Test 303. ’ Phenylhydrazine hydrochloride gives 1-phenylpyra- 
zolon (5) carbonic (3) ac. 

Trimethylenedicarbonic (1, 2) Ac. (fumaroid), Cs H,.(CO,H),.—Glassy 
thls. in. 5 pte: aq.Ag.A d. s. h. aq.— B. p. (30 mm.) abt. 
210°. 





GENUS III, DIV. A, SECT. 1. 49 


(ORDER I, SUBORDER I.) 





Melting-point Neut. [SOLID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in 
(C.°). Equiv. 50 parts of cold water. 





—_——__— 


176 79 =| Cis-3, 3-Dimethyltrimethylenedicarbonic(1,2) Ac., C,;H,,0,—\Tbl. 
rather d. s. c. aq.—Above m. p. gives anhyd., m. p. 56°. Very 
stable towards KMnO, and Br. 


175d. 226 | d-Mannoheptonic Ac., C,H,,0,.—S. in 25 pt. c. aq.—Opt. [—]— 
Cad, s. h. aq.; BaA, d. s. ec. aqg.—Gives Test 302. 
175-8 Glucuronic Anhyd., C,H,O,.—V. s. aq.; 1. ale-—Reduces Fehling’s 
sol.—Ac. syrupy and e. s. alc. 
177 78 | Diacetylenedicarbonic Ac., CO,H.C : C.C : C.CO,H+aq.—Tbl. fr. 


ale.—eth. S. aq.; e. s. ale. or eth._—Turns purplish in light. 
—Ammon. Cu,Cl, gives a red ppt. at 30°. 


178d. 67 | Methyltartronic Ac., Me.COH.(CO,H),.—Rhombic cryst., s. aq.— 
NH, salt ppt’d by boiling BaCl,.—Gives Test 303. 
178-9 57 | Acetylenedicarbonic Ac., CO,H.C : C.CO,H.—(Cryst. w. 2 aq.— 


Cryst. effloresce in air; lose aq. of cryst. over H,SO,).—V. s. aq., 
alc., or eth.—Gives Test 304 easily. Is reduced to succinic ac. 
' (Test 320) by Na amalgam.—Ag. salt v. unstable. BaA-+agq,., 
Ci denC. ac. 
180 80 | s-Methylethylsuccinic Ac. (fumaroid), CO,H.CHEt.CHMe.CO,H.— 
Ndl., 3 pt. s. in 100 pt. aq. at 17°; e. s. eth.; d. s. CHCl;:— 
A 5% sol. of Na,A gives w. c. CaCl, no ppt., but w. h. CaCl, 
cubical cryst., CaA, which disappear again on ‘cooling. 
181d. 91 | Oxyphthalic Ac., C,H, (OH)(CO »H).(4 : 1 :2).—Gives anhyd. on melt- 
ing.—Rosettes Ss. in 32 pt. aq. at 10°; s. eth.—Aq. sol. reddish yel- 
low w. FeCl,.—Fuse for a short time w. some resorcine at 200°: 
Fusion s. in aq. w. greenish fluorescence; KOH turns to dark 
yellowish red. 


183 152 Oxytoluic Ac., C,H;.(OH)(Me)(CO,H)(6: 1: 2).—Ndl. s. ¢. aq.; 
v. s. eth. — FeCl, gives light-brown ppt. a Views: aC. 

184d. 58 { 1,1,2-Trimethylenetricarbonic Ac., C,H;.(CO,H);—Pr. fr. aq.— 
Gives Test 303. 

185 59 | +Succinic Ac., CO,H.CH,.CH,.CO,H.—Monoclinic pr., s. in 14-57 


pt. aq. at 20° , or in Q- 826 pt. at 100° + seale-: dos, eth: 51. CHC, 
or CS, —Distils at 235° giving anhydride! Burns w. blue 
smokeless flame.—CaCl, gives white cryst. ppt. only in cone. 
sols.*of alkaline salts. Ppt. s. in aq., Ac, HCl, or hot NH,Cl 
sol.; 1 -hydroxy acid, gives a somewhat 
similar coloration in Test 302.—Apply Test 320! 

185 105 | Isosaccharic Ac., C,H,,0,—Rhombic cryst., e. s. aq. or alc.; d.s. 
eth.—Aq. sol. shows birotation.—Dec. on dist. —Ag,A, cryst. 
ppt. which gives silver mirror on warming w. ammonia. 

185-7d. (?) 60 | Tartronic Ac., HO.CH.(CO,H),..—(Cryst. w. 4 aq.)—Pr. fr. eth., 

e. s. aq. or alc.; d. s. eth. when not anhyd.—Sbl. at 110°-120°. 
—Gives Test 303, yielding glycolid (ay Dz "990°, —BaA (at me ; 
floc. ppt. changing to lft. v.d.s. h. aq.; Ag,A cryst. ppt. d.s 





h. aq. 
186-8d. 61-5 | Cyclopentane-tetracarbonic(1, 1, 3, 3) Ac., C,H,,0,.— Hygroscopic 
cryst. mass. Gives Test 303. 
189d. 58-5 | (@)-3, 4-Dicarboxyl-hexanedioic(1,6) Ac., C,H,,O,.— Silky ndl. fr. 


aq.— 100 pt. aq. dis. 27-4 pt. at 19°. — In “melting gives an 
anhyd.—Ag,A, amorph. ppt. 

189-5 45 + Oxalic Ac. (Anhydrous), CO,H.CO,H.—Octahedra. Takes on 
water quickly.—S. aq.—For reactions see the hydrated acid on 
p. 42 of this section ! 

191d. 58 + Aconitic Ac., CO,H.CH,.C(CO,H) :CH.CO,H.—Lft. mod. s. ¢. aq 
v.s. alc.; e. Ss, eth. (dif. fr. citric ac.) —Sol. boiled w. x's Ca(OH), 
sol, “gives no ppt. (dif. fr. citric ac.)—BaA,, s. in 24 pts. aq.; 
Ba,A, is ppt.; Zn,A,, i. aq.; Ag,A, floc. ppt. fr. (NH,),A and 
AgNO,.—Gives Test 304 (and 901 slowly, hot).—Reduced by Na 
amalgam to tricarballylic ac. 


50 


GENUS III, DIV. A, SECT. 1. 


(ORDER I, SUBORDER I.) 





Melting-point Neut. |SOLID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in 
COR). 


Equiv. 
192-3d. 66 
195 87 
198-203d. 58 
199d. 154 
199-200d. re 
199-200 154 
199-200 76-7 
201 
abt. 200 
202 65 
204 190 
205-6 84 
208 152 
209 73 
d.210 
213 79 
216d. 70 
218-20d. 65 


50 parts of cold water. 


Dimethylmalonic Ac., (CO,H),.C.Me,.—4-sided pr. s. in 10 pt. ¢. aq.; 


e. s. eth.—Sbl. in ndl. at abt. 120°.—Gives Test 303, yielding CO, 
and isobutyric ac. (cf. Test 311). 


Tetramethylsuccinic Ac.—(Cf. Div. A, Sec. 2.) 


Tetramethylenetetracarbonic(1, 1, 2, 2) Ac., C,H,.(CO,H),.—V.e.s. 
aq., alc., or eth. Gives Test 303. 


Protocatechuic Ac., (OH),.C,H,.CO,H.(3 : 4: 1).—(Loses water of 
eryst. at 100°.)—S. aq.; v.s. alc.; mod. s. eth.—Aqueous sol. + 
FeCl, becomes blue-green; on adding Na,CO, changes to dark 
red !—PbAc gives ppt. s. in dil. Ac—Reduces ammon, AgNO,, 
but not Fehling’s sol.—On distil., or NaOH fusion, gives pyro- 
catechin and CO, (cf. Test 416). 


Camphenic Ac., C,,H,,0,.—E. s. aq. or eth.—Ba salt, v. e. s. aq.; 
Pb, A, (at 100°). 

2, 5-Dioxybenzoic Ac., (HO),.C,H;.CO,H.—Nadl. or-pr., e. s. aq., alc., 
or eth.—FeCl, gives deep-blue coloration! On heating w. FeCl, 
sol. gives CO, and odor of quinone.—BaA,, v. s. aq.; PbA,, v. d. 
s. aq.—Reduces ammon,. AgNO, and Fehling’s sol. when warmed. 
—On distil. dec. to CO, and hydroquinone. 

Camphoic Ac., C,)H,,0,.—Cryst. v. s. aq., ale., or eth.—Gives off CO, 
at 300°.—Pb,A, (at 100°) ppt.; BaA cryst., e. s. aq. 

Camphanic Ac., C,H,,0,.CO,H.—Sbl. fr. 110°.—S. aq.; e.s. alc. or eth, 

+ Tannic Ac., C,,H,,0,.—Cf. III, A, 1, m. p. 210°. 

Mesaconic Ac., Me(CO,H)C:CH.(CO,H).—Ndl. fr. aq. or ale. S. in 
37 pt. aq. at 18°; v.s. hot.—Sbl. undec.! Does not give Test 304 
easily. Warmed w. acetyl chloride gives citraconic anhyd.—NH, 
salt gives brown floc. ppt. w. FeCl; (i. h. or in x’s of reagent).— 
Ca and Ba salts mod. s. aq.—PbA and Ag,A ppts. 

2, 3-Dioxybenzoic Ac., C,H,(OH),.CO,H.2 aq.—S. aq.—Gives blue 
color w. FeCl,, changing to violet w. Na,CO,.—Ba and Pb salts 
v. d. s. aq.—Distil. gives CO, and pyrocatechin. (Cf. Test 416.) 

t+ Racemic Ac., CO,H.(CHOH),.CO,H.—Triclinie cryst. containing 1 
mol. H,O which effloresce in the air !—Hydrated ae. s. in 4-84 pt. 
aq. at 20°, or in 48 pt. c. ale-—Gives Tests 302 and 314! Ppts. 
CaSO, sol. (unlike tartaric ac.); ppt. s. in dil. HCl and reppt’d at 
once by NH,OH (dif. fr. tartaric)—BaA, 23 aq. alm. i. c. aq.— 
Ag,A less s. than tartrate. 

5-Oxy-3-toluic Ac., Me.C,H,OH.CO,H.—Tbl. fr. h. ag. ‘‘Mod. s. ¢. 
aq.”’—Sbl.—PbA, eryst. ppt.; CaA,.2 aq., pr. e. s. aq.—Dist. w. 
CaO gives CO, and m-cresol. 

s-Dimethylsuccinic Ac. (fumaroid), (CHMe),.(CO,H),.—Pr. fr. aq.; 
i. CHC],—Acety] chloride gives anhyd. w. m. p. 43°. 

+ Gallotannic Ac., C,,H,,0, (?).—A light buff-colored powder or scales. 
Taste very astringent!—S. c. aq.; less s. alc.; i. abs. eth.—1 drop 
FeCl, (10% sol.) +20 cc. aqueous tannin sol. (1 : 5000) gives a 
color that is deep blue by transmitted light! Gelatine sol. gives 
immediate white ppt. !—(The last two reactions distinguish from 
gallic ac.) Alkaline sol. quickly absorbs O and becomes brown! 
At 210° gives CO,, pyrogallol, etc.—The salts are amorphous.— 
Reduces AgNO, sol. on boiling. 

trans-3, 3-Dimethyltrimethylenedicarbonic(1, 2) Ac., C,H,,O,.—Pr.e. 
s. h. aq.; d. s. eth.; alm. i. CHCl,—Stable. Heating alone gives 
no anhyd. 

a-Trimellitic Ac., C,H;,.(CO,H),(1, 2, 4).—S. h. aq. or eth.—Gives an 
anhyd. on fusion.—Distil and test distillate for phthalic anhyd. 
by Test 318-1 !—Ba,A,. d. s. aq.—Ag,A, ppt. d. s. aq. 

I, I, 3, 3-Hexamethylenetetracarbonic Ac., C,,H,,0,.—Pr., s. c. aq.; 
e. s. h. ale.; d.s. eth.—Ag,A gelat. ppt.—Dec. on melting to CO, 
and dicarbonic acids. 





Melting-point 
(0.2). 


220 


232 


236 (s. h.) 
237d. 
238d. 
264d. 


286-8 
345-50 


Neut. 


Equiv. 


58 


181 


58:5 


63-5 


63-5 


63-5 


57 
70 


GENUS= Tie DIV A kG Ls 1, 51 


(ORDER I, SUBORDER I.) 





SOLID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in 
50 parts of cold water. 


cis-trans-s-1, 2, 3-Trimethylenetricarbonic Ac., C,;H;.(CO,H);.—S. aq. 


or alc.—Ba,A,+aq. ppt.; Ag,A ppt. 

3, 5-Dioxybenzoic Ac., (HO),.C,H;.CO,H.13 aq.—Pr. mod. s. ¢. aq.3 
e. s. alc. or eth.—Gives no color w. FeCl, and no ppt. w. PbAc.— 
Fusion w. § pts. NaOH gives resorcine (Test 418).—Gives deep- 
red color on heating at 14C° w. 4 pts. conc. H,SO,; ppt’d green 
by aq. 

a-3, 4-Dicarboxyl-hexanedioic(1, 6) Ac., C,H,,O,.—Lft. fr. aq.—100 
pt. aq. dissolve 11-8 pt. at 19°; v.s. alc.; d.s. eth. 

v-Benzenetetracarbonic Ac., C,H,.(CO,H),.—Cryst. w. 2 aq., which it 
loses above 100°. E.s. aq.—Aq. sol. not easily extracted by eth. 
—In melting gives an anhyd.—Crystals resemble prehnite.— 
Pb,A, i. aq.; Me,A, m. p. 104°-8°; Me,A, m. p. 176°-7°.—Aq. sol. 
of acid gives a cryst. ppt. BaA,-+ H,O when warmed w. BaCl, sol. 
(Dif.ir. 1, 2,3, 5 acid:) 

Q-I, 2, 3, 5-Benzenetetracarbonic Ac., C,H,.(CO.H),.— E. s. aq.— 
Conc. HCl ppt’s fr. aq. sol. in short ndl. On melting forms an 

‘ anhydride.—Gives floc. ppt. w. PbAc,; floc. pp. w. CaAc, on heat- 
ing; floc. ppt. w. BaO,H,, but none w. BaCl,. 
s-Benzenetetracarbonic Ac., (Pyromellitic Ac.), C,H,.(CO,H),—In 
melting gives an anhydride.—Triclinic tbl., 100 pt. aq. dissolve 
14-2 pt. at 16°; e. s. ale.—Sbl. giving anhyd. m. p. 286°.—Ca, 
Pb, and Ag salts are ppts.—Me,A, m. p. 138°. 

Mellitic Ac., C,.(CO,H),.—Fine silky ndl., v. e. s. aq.; e. 8. ale. 

(s)-1, 3, 5-Irimesic Ac., C,H,.(CO,H),.—Pr. fr _aq.—‘‘ Moderately” 
s. ¢. aq.; v. 8. ale.—Sbl. below 300° —Ba,A,-aq., lustrous ndl., 
alm. i.c.aq.; v.d.s.h.aq.; Zn;A, pr. alm.i.c.aq.; Ag;A, volum. 
ppt.—Me,A, m. p. 143°. 


COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I}. 
GENUS IIL, ACIDS. 


DIVISION A, SECTION 2,—SOLID ACIDS NOT SOLUBLE IN COLD 
WATER. 





Melting-point Neut. [SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 
(C.°). Equiv. in 50 parts of cold water. 





14 282 | { Oleic Ac., C,,H,,0,.—B. p. 232° (20 mm.).—G. 0-89081!"8/,.—Gives 
Tests 304 and 901! Absorbs O from the air.—Fused in a test- 
tube w. x’s of moist KOH in a bath the temperature of which is 
gradually raised from 300°-320°, is converted almost quanti- 
tatively into potassium palmitate, acetate, and H.—Dilute one 
volume of the nitrosyl-sulphuric ac. reagent described on p. 13 
with one vol. of aq., and shake the mixture in a test-tube with 
an equal volume of the oily acid, keeping it well cooled with run- 
ning tap-water. Set the tube aside in a beaker containing cold 
water for 15 minutes. A solid mass of elaidic ac. (m. p. after 
purification 51°—2°) soon separates. 

16-7, 298 | Ricinoleic Ac., C,,H,,0;—B. p. 250° (15 mm.).—Gives Tests 304 
and 901.—Treatment w. nitrosyl-sulphuric acid, as described 
under oleic ac , gives ricinelaidic ac., m. p. 50°.—Polymerizes 


easily. 

19-4 166 | Ethylethersalicylic Ac., EtO.C,H,.CO,H.—D. s. c., e. s. h. aq.— 
BaA, Vv. s. aq. 

21-3 181 | Umbellulic Ac., C,,H,.0,.—Cryst.—B. p. 275°-80° c.—(An ac. fr. 
fat of Californian Laurel.) 

24-4 114 | 2-Methylpenten(2)-oic(1) Ac., C,H,,0,—B. p. 213° c.—V. d.s. aq.; 
e. s. eth.—Gives Test 304.—Is volat. w. steam.—AgA, ndl. or 
tire pad. 

94-5 184 | t Undecylenic Ac., Me.C,H,.C,H,,.CO,H.— B. p. 165° (15 mm.).— 


(From distil. of castor-oil i. v.)—G. 0-9072 *4/,.—BaA,. ndl. or lft. 
s. in 1073 pt. aq. at 15-5°.—Fuming HNO, oxid. to sebacic ac.— 
Gives Tests 304 and 901! 


26 344 | Anacardic Ac., C,.H,.0,,—(From Anacardium occidentale.) I. aq.; 
e.s. ale or eth.—AgA (at 100°) ppt. fr. alc. sol. by AgNOs. 
26-7 256 | Diheptylacetic Ac., CH(C,H,,),.COOH.—Cryst., alm. i. aq.; Vv. €. s. 
alc., eth., or bz.—BaAy, fine ndl. fr. alc.; i. aq. 
28-5 186 Undecylic Ac., C,,H,,0,.—Scaly cryst. mass.—B, p.212-5° (100 mm.). 
—Feeble odor like caproic ac.—RaA,, v. d.s.; Aga, 1. aq. 
29 Triethyl Methanetricarbonate, HC.(CO,Et);.—B. p. 253°.—Ndl. or 


pr.—‘‘Is saponified at 0° by KOH to alcohol, CO,, and malonie 
ac.” ! §. in NaCoO, sol. 

30 Acetylperoxide, (Me.CO),.0,.—Flat cryst. w. odor like ozone. 
‘Somewhat’? s. aq.—Extremely explosive-——NaOH gives Ac, 
and sodium peroxide. 


30 128 | Hexahydrobenzoic Ac., C,H,,.CO,H.—B. p. 233°.—D. s. aq.; V. Ss. 
ale. or eth.—ZnA, much more s, in c. than in h. aq.—Volat. w. 
steam. 

31 176 | Cinnamenylpropionic Ac., Ph.CH,.CH:CH.CH,.CO,H. — Tbl. fr. lgr. 
—Gives Test 304.—BaA,, d. s. aq.; AgA ppt. 

31-3 172 | + Capric Ac., Me.(CH,),.CO,.H.—B. p. 268-4° c.—Feeble odor like 


perspiration.—Alm. i. ¢. aq.; Vv. d. s. h. aq.—Alkali salts alone 
soluble.—BaA,, lft. fr. h. aq.—G. 0-93 at 37°. 


(igre a enn 
52 


Melting-point 
COs 
33 


33 


33:4 


45-5 


46-7 


Neut. 
Equiv. 


GENUS Ill; DIV. A, SECT. 2. | 53 


(ORDER I, SUBORDER 1.) 


SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 
in 50 parts of cold water. 








254 


114 


338 


136 
270 
127 
164 


214 
114 


164 
113 


166 
200 
240 


282 


100 





Hypogeic Ac., C,,H,,0,—Ndl. e. s. ale—B. p. 236° (15 mm.).— 
Oxidizes in air.—Nitrous acid (cf. oleic ac.) gives gaidic ac., m. 
p. 39°. Gives Test 304. 

Hexen-2-oic-(1) Ac., C,H,,0O,.—Ndl. d. s. ag.—Adds Br, in CS, sol. 
(Test 304).—Baa,+ 14 aq,, lft.; e. s. ale.; AgA, ndl. fr. aq. 

t Erucic Ac., C,,H,,.CO,H.—Long ndl. fr. ale. B.p. 264° (15 mm.), 
Gives Test 304 !—Heated to fusion w. dil. HNO, and treated w. 
NaNO, gives geomet. isomer, brassidic ac., which after cryst. fr. 
alc. melts at 60°.—PbA,, e. s. h. eth. or h. bz. 

p-Methylenedihydrobenzoic Ac., CH,:C,H,.CO,H.—Ndl. fr. lgr. S.h. 
aq.; e. Ss. ale. oreth. Gives Test 304.—AgaA silky ndl. 

Oxyhypogeic Ac., C,,H;,,0,;—White mass.—Boiling alkalies give 
dioxypalmitic Ac. 

o-Toluic Anhyd., (Me.C,H,.CO),..0.—R. p. a. 325°.—Cryst. fr. eth. or 
bz.—Test 307 gives ac. w. m. p. 102°, v. d. s. c. aq.! 

a-Methylhydrocinnamic Ac., Ph.CH,.CHMe.CO,H.—B. p. 272°, Lft. 
v. d. s. c. aq.— Ag, cryst. ppt. 

Tridecylic Ac., Me.(CH,),,.CO,H. 

a-Ethylcrotonic Ac.—C,H,,0,.—Cryst.—Sbl.—D. s. aq.—Fusion w. 
KOH gives acetic and butyric acids. (Test 311.) 

Ethylphenylacetic Ac., Ph.CHEt.CO,H. 

7 Benzoic Anhyd., (C;H,O),.0.—B. p. 360° c.—Rhomb. pr. i. and 
very slowly attacked by c. aq.; s. ale. or eth. For behavior on 
titration cf. p. 37. Test 307 gives ac. (cf. Test 312) w. m. p. 
121°, nearly i. c. aq.! 

o-Oxyphenylgiyoxylic Ac., HO.C,H,.CO.CO,H.—Ndl. Dec. on dist. 
to CO, and salicylic ac. (Test 319). 

t Lauric Ac., C,,H,;.CO,H.—Ndl. fr. ale-—Dec. by dist. under normal 
pressure.— Non-alkali salts all v. d. s. h. aq.—BaA,, pearly lft. 
Cimicic Ac., C,,H,,O,.—Pr. fr. eth—BaA,. amorph. ppt.—Unsat. 

(Test 304). 

Isooleic Ac., C,;H;,.CH:HC.CO,H.—Rhomb. plates fr. eth—E. s. 
alc.; less s. eth.—ZnA, cryst. fr. h. alc. (sep. fr. oleate). PbA, 
less Ss. in eth. than Pb oleate-——Occurs in some commercial 
‘“stearic ac.” 

Angelic Ac., Me.CH.MeC.CO,H.—B. p. 185° (th. i.). Long-con- 
tinued boiling gives isomeric tiglic ac., m. p. 64-5°.—Pr. d. s. ¢. 
aq ; e. 8s. h. aq.—Spicyv odor.—CaA,+2 aq. alm. i. alc.; s. ¢. aq.; 
much less s. at 60°-70°.—BaA, +43 aq., e. s. aqg.— PbA, d. s. aqg.— 
Fusion w. KOH gives acetic and propionic acids (Test 311). 

Paraffinic Ac., C,,H,,0,.—Lft. fr. ale-—(Fr. action of fuming HNO, 
on paraffin.) 

Diisoamylacetic Ac., (C;H,,),..CH.CO,H.—Ndl. i. aq.; e. s. eth., alc. 
or bz. 

m-Ethylbenzoic Ac., Et.C,H,.CO,H.—Ndl. fr. h. aq., alm. i. ce. aq.— 
CaA, e. s. aq. or ale.—Test 905-1 gives isophthalic ac. 

Palmitolic Ac., C,,H,.0,.—B. p. 240° (15 mm.). Silky ndl.; i. aq.; 
v. s. ale. or eth_—Fuming HNO, oxid. violently.—BaA,, cryst. 
fr. h. alc.; i. aq.—AgaA, ppt., blackens in light.—Gives Test 304. 

Benzylpropionic Ac., Ph.(CH,),.CO,H.—Flat lft. fr. h. aq.; e. s. ale. 
or eth.—B. p. abt. 290°.—-CaA,, v. s. aq.; BaA,, Ift., s. aq. 

Stearolic Ac., C,.H,,0,.—Long pr. fr. ale-—D. s. c. ale.; e. s. h.— 
Distils w. little dec.—Gives Test 304.—Oxid. by fuming HNO,,. 
—BaA,, ppt. fr. aq.; s. h. ale. ; 

Diallyloxalic Ac., HO.C(C,H,),.CO,H.—Ndl. ‘‘rather d.” s. aq.; e. S. 
ale. or eth.—Gives Test 304.—Dec. on distil—Ca and Ba salts, 
e. S. C. aq. = 


—_————— eS 


54 





Melting-point Neut. 
(G2). Equiv. 
48-7 150 

50 298 
50 310 
Sy 242 
51 244 
51 164 
51 296 
OL 258 
51-5 282 
52 178 
53 168 
53-8 228 
54-6 338 
54-5 270 
56-7 49 
56-7 57 
OF 148 
57-5 336 
58 164 
58-9 178 
59-5 182 
59-9 270 
60 or 65 146 
60 338 
61 150 
62-6c 256 





GENUS, DIV, A, SECT, 2. 


(ORDER I, SUBORDER I.) 





SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 
in 50 parts of cold water. 





Hydrocinnamic Ac., Ph.CH,.CH,.CO,H.—B. p. 279-8° (th. i.).— 
Ndl. fr. ale. or h. aq.; s. in 168 pt. aq. at 20°.—BaA,, mod. s. ndl. 
—Boiling with CrO, mixture (cf. Test 702) gives benzoic ac, 
(cf. Test 312). 

Ricinelaidic Ac., C,,H,,0,.—Ndl.—Oxid. by HNO, gives cenanthic ac. 

Eikosenic Ac., C,,»H;,,0,.—B. p. 267° (15 mm.) (th. i.).—Gives Test 
304.—BaA,. Cryst. fr. ale. 

Pentadecylic Ac., C,;H ,0,.—Dec. on distil—Pearly scales. 

Oxymyristic Ac., C,,H,,0,.—Pearly lft., e. s. ale-—Dec. on distil._— 
Ca and Ba salts, ppts., d. s. h. aq. 

o-Isopropylbenzoic Ac., Pr.C,H,.CO,H.—Pr. s. h. aq.—Ba salt vy. s, 
aq.—lest 905 gives phthalic ac. (cf. Test 318-1). 

Ricinostearolic Ac., C,,H;,.0;—Ndl. fr. alc.—I. aq.; e. s. alc. or eth. 
Gives Test 304. Volatile w. very slight dec.—BaA, lft. fr. alc.; 
i, eth—AgaA gran. ppt.; i. eth. 

Oxypentadecylic Ac., C,,H.,0,.—Ndl. fr. dil. ale. (From convolvulin.) 

+ Elaidic Ac., HC. (C,,Hus) : HC.CH,.CO,H.—Lft. fr. ale-—Solidifies at 
44°_45°, on) p. 234° (15 mm.). Bai, PbA, are ppts.—(Geom. 
isomer of oleic ac.) 

1-Methoethylphenethanoic(4) Ac., Me,.CH.C,H,.CH,.CO,H.—Ndl. fr. 
h. aq.—V. s. ale. or eth.—CaA, heated w. CaO gives cymene. 

{-Campholenic Ac., C,,H,,0,.—B. p. 247°.—Gives Test 304.—I. aq.; 
v. s. ale. or bz. BE Cy es ndl.,e. s. alc.; d.s. aq. 

{ Myristic Ac., C,,H,,0,.—Lft. a SG, Ate or eth.—B. p. 196-5° (15 
mm,).—BaA, cryst. powder; v. d.s. alc. or aq.; Pb, amorph, 
powder. 

Isoerucic Ac., C,.H,,0,.—Tbl. fr. alc.; rather d. s. ale. or eth.—Adds 
Br, in glacial Ac. sol. (Test 304.) 

Daturic Ac., C,;H,,0,.—Small ndl. fr. ale.; i. aq.i— PbA,, m. p. 104°-5°. 

Maleic Annede C,H,O;.—Cryst. melt eee h. aq., gradually giving 
maleic ac.—Ac. obtained by Test 307, v. s. aq., m. p. 130°. 

Glutaric Anhyd., C,H,O,.—B. p. 287° c.—Ndl. d. s. h. eth—Acid 
obtained by Test 307, s. aq.; m. p. 97-5°. 

Isocinnamic Ac., HCPh : HC.CO,H.—Monoclinic pr. fr. lgr.—v. s. 
ale., eth., or Igr. —Gives Test 304.—On continued boiling gives 
cinnamic ac. (Test 313) and styrene.—CaA,, s. in 8 pt. aq. 

Behenolic Ac., C,.H,,0,.—Ndl. e. s. abs. ale.—Gives Test 304.—Zn. 
dust and acetic ac. reduces to brassidic ac.—BaA, ppt. i. aq. and 
alc. 

o-Propylbenzoic Ac., Pr.C,H,.CO,H.—Lft. fr. dil. ale—Test 905 
gives phthalic ac. 

0-Phenylvalerianic Ac., Ph.(CH,),.CO,H.—Lft. fr. h. aq., e. s. ale.-— 
Ba salt d. s. aq. 

Undecolic Ac., C,,H,,0,.—Lft. e. s. ale——BaA, v. d. s. c. aq.—B. p. 
177° (15 mm.). Gives Test 304. 

Margaric Ac., C,,H,,0,.—Cryst. 

Pecan aiiistts Ac., Me.(CH,),.CHOH.CO,H.—D. s. c. aq.—Sbl. 

Brassidic Ac., C,.H,,0,.—Lft. fr. ale —B. p. 160° (0 mm.) —V. d.s. ec. 
alc.—Less s. in alc. or eth. than erucic ac.—PbaA, v. d. s. h. eth.— 
JKOH fusion gives arachidic ac., m. p. 77°—Gives Test 304. 

m-Tolyacetic Ac., Me.C,.H,.CH, .CO,H.—Ndl. e. s. h. aq.—AgA, ndl. 
fr. hag. —Amide, ity 0 141° 

t Palmitic Ac., Me.(CH,),,.CO,H.—Ndl. or greasy feeling scales, s. in 
10-7 pt. ale. at 20°; e.s. h. pipe) p. 339°-56° d.—G_ 0-8527 epee 
—Nearly odorless and tasteless. N early or quite neutral to in- 
dicators excepl in alc. sol. 





ng ee ee 


Melting-point 
(C.°); 


64 
64-5 
65 


66-5 
67 


68 


68 


68 


69 
69-5 


69-3c. 


71-2 


77 





Neut. 
Equiv. 


330 
100 


162 


308 
160 


284 


144 


180 


166 


142 
162 


180 


296 


208 


178 


214 
136 


312 


GENUS III, DIV. A, SECT. 2. 55 


(ORDER I, SUBORDER I.) 








SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 


in 50 parts of cold water. 


Dioxyricinoleic Ac., C,,H;,0;—I. aq.; v. e. s. ale. or eth.—Gives 





ee UUEEEEEEEEEE EEE 
00 OO 


Test 304. 

Tiglic Ac., Me.CH:CMe.CO,H.—Gives Test 304; and 901 (slowly 
hot).—Cf. Div. A, Sec. 1. 

(a?)-Phenylcrotonic Ac., Ph.CH,.CH : CH.CO,H.—Nadl. fr. h. aq., e. 
s. ale., eth., and bz.—Gives Test 304.—CaA,+3H.0 silky ndl. 

Nondecylic Ac., C,,H,,0..—CaA,, cryst. ppt. 

Palmitoxylic Ac., C,,H,,0,—I. aq.; e. s. abs. alc. or eth_—AgaA gran. 
ppt. fr. alc. 

Itaconic Anhyd., C;H,O,.— Dist. in vacuo gives citraconic anhyd., m. 
p. 7.°—Rhomb. pr. tr. CHCl,; v. d.s. eth.—Unites rather easily 
w. aq to form its acid (cf. Test 307). 

o-Ethylbenzoic Ac., Et.C,H,.CO,H.—Lustrous flat ndl.—Test 905 
gives phthalic ac. (cf. Test 318-1). 

Allocinnamic Ac., HCPh : HC.CO,H.—Pr. or tbl. fr. lgr.—Aniline salt 
ppt’d fr. bz. solution by aniline, m. p. 83° (Dif. fr. hydrocinnamic 
ac.)—Less s. c. lgr. than isocinnamic ac —Gives Test 304. 

Eikosinic Ac., C,,H;,0,—1I. aq.—B p. 270° (15 mm.). 

a-Oxycaprylic Ac., Me.(CH,) ,., CHOH.CO,H.—Large plates, v. d.s.aq.; 
e. s ale. or eth.—CrO, mixture oxid. to cenanthol and cenanthic 
ac.—Salts generally d. s. 

+ Stearic Ac., Me.(CH,),,.CO,H.—Odorless, tasteless Ift.—Distils w. 
dec. at abt. 360°.—I. aq.; s. 40 pt. c. alc.; e. s. ¢ eth., bz., CS, 
or CHCl,.—Does not dissolve on shaking w ec. Na,CO, or deci- 
normal KOH.—CaCl, and BaCl, give gelat. ppt. w solutions of 
alkali salts. 

Monoethyl Fumarate, CO,H.C,H,.CO,Et.—D s. aq.; e s. alc. or eth. 
Gives Test 304.—Saponify and identify the fumarie ac. 

3-Methtoethylphenol(2)-methanoic(1) Ac., C,,H,,0,—Ndl. fr. aq.— 
V.d.s.aq.; e s. ale. or eth.—Volat. w. steam.—Aq. sol. intense 
violet-blue w. FeCl, !—AgA mic. ndl. d. s. aq. 

Methoxyphenylacetic Ac., Ph.CH(OMe).CO,H.—Tbl. fr. lgr D.s. 
aq. orc. lgr.; e. s. alc. or eth.—CaA,, ppt., rather d. s. c. aq. 

Carnaubic Ac., C,,H,,0,.—(Combined in Carnauba wax.)—E. s. alc. 
or eth.—PbA, (103°), ppt. m. p. 110°-1°; i. eth. 

y-Ethoxy-4’-tetrahydrobenzoic Ac., EtO.C,H,.CO,H.—E s ale.— 
Gives Test 304.—AgA, ppt. 

a-Benzalpropionic Ac., Ph.CH : CMe.CO,H.—B. p. 288° Cryst.e s. 
ale., eth., or bz.—Gives Test 304—BaA,, d.s.c aq 

Phenyl-1’-cxybutyric Ac., Ph.CHOH.(CE,),.CO,H.— Pr. fr. c CHCl. 
—S. h. aq.; v.e.s. ale, eth., or CHCl;—Aq.+ HCl at 80° gives 
anhvd., m. p. 37°.— BaA,, v s aq.; AgA, ppt.,i aq. 

Dioctylmalonic Ac., C,,H,,0,—Cryst. fr bz—CaA, d.s. aq.—Gives 
Test 303. 

a-Hydropiperic Ac., C,,H,,0,. —Ndl.fr h.aq.—V.d.s ¢ aq.-e s ale 
or eth.—KMn0O, oxid. to piperonal (odor like heliotrope'), ete. 
Gives Test 304 —AgaA cryst. ppt 

1-Methyl-3-propylbenzoic(4) Ac., (Me)(Pr).C,H;.CO.H.—Ndl fr. aqg.— 
Volat. w steam.—Ba and Ca salts v s aq. or ale, 

Lanolic Ac., C,.H,,0,.—Cryst powder.—I. aq. or lgr —BaA,+aq. ppt. 

{ Phenylacetic Ac., Ph.CH,.CO,H.—B. p 265-5° ¢ —Thin Ift e s. h. 
aq.; d.s c aq.; v s. alc. or eth—BaA,+3H,0, e.s. aq. or alc. 
BaCl, gives no ppt Warming w dil. H,SO, and MnO, gives 
benzaldehyde (bitter almond odor, Test 113). 

Arachidic Ac., C,,H,,0,.—Lustrous lft., s in 222 pt 90% alc. at 20°. 
(Less s. than stearic ac.)—Salts resemble stearates.—Occurs in 
peanut-oil, etc. 








Melting-point 
(Ccy 





77-8 
78 
78 

78-80 
80 


80-1 


87-8 


88-9 


88-9 


89 
90 


382 


Neut. 
Equiv. 


396 


312 


176 


194 


368 


162 


272 
106 


300 


340 
300 


314 
176 
218 
312 


162 


204 


56 


240 


64 


272 


178 


150 


282 
452 


ee ee ee 


GENUS III, DIV. A, SECT. 2. 


(ORDER I, SUBORDER I.) 





SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 


in 50 parts of cold water. 





Hyenic Ac., C,,H,,O,.—Cryst. grains. 

Cerotic Ac., C,,H,,0,.—(In beeswax.)—Tasteless and usually granular. 
—Alm. i. c. alc. (dif. fr. stearic and palmitic ac.).—Stellate mic. 
ndl. fr. h. ale-—S. bz. or eth.—Does not dissolve in h. dil. NaOH. 

Ricinstearoxylic Ac., C,,H;,0,.—Ndl. e. s. ale. or eth.—Gives Test 
304.—BaA,, volum. ppt.; AgA, gran. ppt. 

Pinoylformic Ac., C,,H,,O,.—Lft. fr. h, aq.; v. s. h. aq.; e. s. eth.— 
Gives soluble KHSO, compound. 

y-Methylhydrinden-{-Carbonic Ac., C,,H,,0..—B. p. 300°-30°.—S. h. 
aq.; e. s. ale—BaA,+4 aq., ndl., v. s. aq. 

o-Ethylethermelilotic Ac., o-EtO.C,H,.C,H,.CO,H.—Silky ndl. fr. aq.; 
v.d.s.c., d.s. h. aq.; e. s. alc. or eth.—Ba salt, e. s. aq. turns red 
at 100°. 

Lignoceric Ac., C,,H,,0,.—D. s. c. ale.; e. s. eth., bz., or CS,.—Pearly 
lustre, 

a-Benzalpropionic Ac., Ph.CH : CMe.CO,H.—Repeated recryst. gives 
ac., m, p. 74°. Gives Test 304. 

Mono-methyl Phthalate, C,H,0,. Examine saponification products. 

a-Oxypalmitic Ac., C,,H».CHOH.CO,H.—Sceales fr. alc.; e. s. ale. 

Monoethyl1 Carbopyrotritarate, C,H,0,.Et. —D. s. h. aq.—Lft. e. s. eth.; 
e. s. alc. Distil. undec.—AgaA ppt. 

f-Oxystearic Ac., C,,H;,0;.—6-sided tbl. fr. ale. S. in 10-4 pt. ale. 
at 20°. 

Behenic Ac., C,,H,,0,.—Solidifies at 78°. 

a-Oxystearic Ac., C,,H;,0;.—6-sided tbl. fr. eth. §S. in 172 pt. ale. 
at 20°. 

Ketostearic Ac., C,,H;,,0,.—Silky cryst. fr. dil. ale—AgA, cryst. ppt. 

Ac.-Tetrahydro-a-Naphthoic Ac., C,,H,,.CO,H.—Pr. fr. acetic ether. S, 
in 1052 pt. c. aq.; v. s. ale—KMnO,+ Na,CO,; sol. decolorizes after 
2 min.—AgaA ppt. 

Dioxyundecylic Ac., C,,H,,.0,—Ndl. fr. aq.; e. s. h. aq. orale.; d.s. eth. 

Stearoxylic Ac., C,,H;,0,—Lft. d.s. ¢. alc.; e. s. h. ale-—BaA, semi- 
solid ppt., i. ale.; AgA cryst. powder. 

$-Benzalpropionic Ac., Ph.CH : CH.CH;.CO,H.—B. p. 302° (long-con- 
tinued boiling gives H,O and a-naphthol, Test 402).—Ndl. fr. h. 
aq.; d.s. h.aq.; e. 8. alc., eth., or CS,.—-CaA, v. s. aq. 

Monomethyl Camphorate, CO,H.C,H,,.CO,.M .—Long ndl. fr. h. aq.; 
e. s. alc. oreth.— Saponify and test distillate for methyl alcohol 
by Test 819. re 

Glutaconic Anhyd., C,H,O,.—Nadl. fr. eth., s. in Na,CO, w. efferves- 
cence, giving sodium glutaconate (m. p. of acid 138°). 

Dibenzylacetic Ac., (Ph.CH,),.CH.CO,H.—Pr. fr. lgr.; i. aq.; s. eth.— 
BaA, ndl. d. s. h. aq.—Heated w. CaO gives dibenzylmethane. 

s-Dimethylsuccinic Anhyd. (a), C,H,O;.—RB. p. 235°.—S. h. aq. giving 
s.fumaroid acid, m. p. 124°, and a little less s.-anti acid, m. p. 195°, 

Lanopalmitic Ac., C,,H,,0;—(In combination in wool grease.)—I. in 
aqueous KOH, s. in ale. 

(a) o-Methoxycinnamic Ac., MeO.C,H,.CH:CH.CO,H. —E. s. ale.— 
Heat gives isomeric () ac., m. p. 182°-3°.—Gives Test 304. 

o-Tolylacetic Ac., Me.C,H,.CH,.CO,H.—Silky ndl., e. s. h. aq—Amide 
m. p. 161°.—Oxid. to phthalic ac. by KMnO, (cf. Tests 905-1 
and 318). . 

Dibenzylacetoacetic Ac., C,,H,,.0;. 

Melissic Ac., C3 >H,.0,.—Silky scales (fr. beeswax).—E. s. CHCl,, CS,, 
and h. ale.; alm. i. c. ale. or eth.—PbA,, amorph. ppt.; may be 
ervst. fr. toluene. 





Ee 


GENUS III, DIV. A, SECT. 2. 57 


(ORDER I, SUBORDER I.) 





Melting-point 
.C.°). 


91 


91 


95-7 


95-5 
96 
96-5 
96-7 
97-9 
97 


98 


98-9 


99 


Neut. 
quiv. 


150 


174 


328 
178 
180 
466 
226 
250 


176 


boty. 


164 
240 
07 


468 
356 
150 
166 


154 


206 


372 


184 
162 


164 


176 


316 





SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 


in 50 parts of cold water. 





p-Tolylacetic Ac., Me.C,H,.CH,.CO,H.—B. p. 266°.—Ndl., d. s. c. aq.; 
e. s. h—AgaA ndl., e. s. h. aq.—Amide, Ift. fr. h. aq.; m. p. 184°! 

a-Dihydronaphthoic Ac. (labile), C,,H,,O,.—Tbl. fr. lgr.; s, in 552 pt. 
c. aq.; e. Ss. ale. or eth.—Gives Test 304.—Boiling w. dil. NaOH 
gives stable form, m. p. 125°, 

Fikosanol(2)-oic Ac., C,,H,,0;.—Silky lft. fr. bz.+lgr.; e. s. ale— 
BaA, (at 100°) floc. ppt. 

Tolylisobutyric Ac., C,H,.CH,.CHMe.CO,H.—wNadl. fr. lgr.—AgA, ppt 
v. d. s. aq. 

Methylethermelilotic Ac., o-MeO.C,H,.C,H,.CO,H.—Pr. fr. h. lgr.— 
Dee act: 

Coceric Ac., C;,H,.03;,—Cryst. powd. fr. h. alec. 

o-Benzoylbenzoic Ac., Ph.CO.C,H,.CO,H.—Triclin. ndl. (+aq.) fr. 
h. aq.—Ignited w. Zn dust gives anthracene (Test 912).—Oxime 
melts at 162°. 

Alantolic Ac., HO.C,,H,,..CO,H.—Ndl. d. s. c. aq.; e. s. alc. or eth.— 
Loses aq. on fusion giving anhyd., helenine, m. p. 76°. 

$-Tetrahydronaphthoic Ac., C,,H,,.CO,H.—Nadl. fr. dil. ale.; 1.¢. aq.— 
Adds Br, in the cold, but is not immediately oxid. by Na,CO,+ 
KMn Q,. 

4-Methoethylphenol(2)-methanoic(1) Ac., Me,.CH.C,H,OH.CO,H.— 
Lft. fr. aq., v. d. s. c. aq.; s. h. aq.; v.s. alc. or eth.—Red-violet 
color w. FeCl,.—Distil. gives CO, and m-propylphenol.—BadA, 
asad, 

p-Toluylcarbonic Ac., Me.C,H,.CO.CO,H.—I. c. aq.; e. s. ale. or eth.— 
Unstable.—Conc. H,SO,+bz gives deep-red sol. changing to blue- 
violet; red ppt. on dilution.—Oxid. by KMnQ,. 

Benzyl-o-tolylacetic Ac., (C;H,),.CH.CO,H.—Large cryst. fr. ale. 

3, 6-Dimethylphthalic(1, 2) Ac., Me,.C,H,.(CO,H),.— Pr. e. s. eth. or 
ale. ‘‘ Moderately” s. aq. 

Oxymelissic Ac., Cs).H,.0;.—Fine ndl. fr. bz. 

a-Oxybehenic Ac., C,.H,,0;.—E. s. high-boiling petroleum ether. 

ac 3-Dimethylbenzoic(2) Ac., Me,.C,H;.CO,H.—Nadl. fr. h. aq. 

Alorcinic Ac., C,H, ,0;.+H,O (air-dried).—Ndl. d. s. c. aq.; e. s. ale. 
or eth. Alkaline sol. becomes cherry-red on standing in air! 
Reduces Fehling’s sol.—Fusion w. 3 pt. KOH gives orcine. Dried 
over H,SO, melts at 115°. 

Methyluvinic Ac., C;H,O.CO,H.—Ndl. d. s. aq.; e. s. alc. or eth.— 
CaA,+4 aq., pearly lft. i. ale-—Boiled w. conc. KOH gives potas- 
sium acetate (Test 311). 

Benzyllevulinic Ac., C,,H,,0;—B. p. 230°-35° (40 mm.). Ndl. fr. 
dil. alc., v. d. s. aq.—Dec. on dist.—H,SQ, sol. yellow, but after 
1 or 2 days blue-green.—Dibrom. derivative fr. Br in Ac., m. p. 
ibe ad: 

Isodioxybehenic Ac., C,,H,,0,.—Tbl. fr. alc., d. s. c. alc. or eth— 
AgA ppt. 

[—] Pinonic Ac., C,,H,,0;—B. p. (12 mm.), 178°-80°. 
Methylethersalicylic Ac., o-MeO.C,H,.CO,H.—TDbl. or pr. s. in 200 pt. 
aq. at 30°.—Baa,, v. e. s. aq.—Deec. a. 200° to CO, and anisol. 
s-Dimethylphenylacetic Ac., Me,.C,H;.CH,.CO,H.—B. p. 274°.—Mod. 

s. h. aq.—CaA,+3 aq., e. 8. aq. 

Benzoylacrylic Ac., C;H,0.C,H,.CO,H.—Ndl. fr. toluene, d. s. c. aq.; 
e. s. ale. or eth.—On warming w. alkali gives acetophenone (Test 
712).—Heated above m. p. becomes ruby-red.—Gives Test 304. 

Dioxystearic Ac., C,,H;,0, (from elaidic Ac.).—Alkaline perman- 
ganate gives azelaic, pelargonic and oxalic acids. 








58 GENUS IIL) DIVA “SHOT 


(ORDER I, SUBORDER I.) 





Mettioe noi Neut. {SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 
re, 





Equiv. in 50 parts of cold water. 
100-5 208 | Acetylphenyl-{-lactic Ac., Ph.CH.(MeCO,).CH,.CO,H.—Pearly scales. 
—Dec. at 200° to acetic and cinnamic ac. (Test 313). 
102 164 | o-Tolylpropionic Ac., Me.C,H,.C,H,.CO,H.—S. h. aq.—H,SO, gives 
o-methylhydrindon. 
102 136 | o-Toluic Ac., Me.C,H,.CO,H.—B. p. 259° (th. i.).—Ndl., mod. s. h. aq.; 


v. s. ale.—Test 905-1 or 3 gives phthalic ac. (Test 318).—BaA e, 
s. aq.—Amide melts at 138°. 


102 164 1, 3-Dimethylphenethanoic(4) Ac., Me,.C,H;.CH,.CO,H.—B. p. 265°. 
—Ndl. e. s. alc. or eth. AgA + Aq. e. s. h. aq. 
102-2-5 194 | Meconin, C,,H,,O, (anhydride of meconic ac.).—Sbl.—Ndl. s. in 700 


pt. c. aq. or 22 pt. h. aq.—Contact w. alkalies gives salts of meconic 
ac. (free ac. unknown); is not soluble in ammonia.—Found in 
mother liquors from opium alkaloids.—Heated w. dil. H,SO, and 
MnO, gives opianic ac. 
103 192 | (a), o-Ethoxycinnamic Ac., EtO.C,H,.CH:CH.CO,H.—Tbl. v. d. s. 
d. s.h.aq.; e.s. ale. or eth.— BaA, + 2 aq. e. s. aq.—Heat gives 


oh, 
f-ac., m. p. 135°.—Gives Test 304. 

103-4 184 | i-Pinonic Ac., C,,H,,0,—Lft. fr.aq. ‘‘ Rather’ d.s. c. aq.; e.s. alc. or 
eth.—M. p. of oxime 150°. 

103-4d. 164 Benzoylacetic Ac., Ph.CO.CH,.CO,H.—D. s. aq.; v. s. ale. or eth.— 


Ale. sol., colored violet by FeCl, !—Boiled w. KOH sol. gives ben- 
zoic ac. (Test 312), and acetophenone. Melts w. dec. to CO, and 
acetophenone (Test 712)! Attacked by Br or alk. permanganate. 


104 176 | Phenylangelic Ac., Ph.CH:CEt.CO,H.—Ndl. v. d. s. e. aq.—CrO; 
mixt. oxid. to benzaldehyde and benzoic ac.! Gives Test 304. 
104 176 | Phenylpenten(4)-oic Ac., Ph.C,H,.CH:CH.CO.H.—Tbl. fr. eth., d. 
s. aq.; e. s. eth.—Gives Test 304.—CaA+3H,0O, ndl. d. s. aq. 
104—5d. Lanoceric Ac., C3,H,.0,.—Mice. lft. fr. ale.; d.s.eth. (In combination 
in wool fat). 
105 174 | @-Dihydronaphthoic Ac., C,,H,,O,.—Pr. s. in 1734 pt. aq. at 14°.— 


Oxid. by KMnO, to phthalic ac. In C8, sol. changed by Br to 
bromanhydride m. p. 140° d. 

105 170 | Campholic Ac., C,,H,,0,.—B. p. 260°.—Lft. fr. eth.-ale.; alm. i. aq- 
Volat. w. steam.—Ppt’d fr. sol. of alkali salts by CO,.—Fuming 
HNO, gives camphoric and camphoronic acids.—CaA,+H,0, 
cryst. ppt. 

106 94 | + Azelaic Ac., CO,H.(CH,);.CO,H.—B. p. a. 360° (sl. d.).—Lft. e. s- 
h. aq.; s. in 700 pt. aq. at 15°.—5S. in 37 pt. c. eth_—CaA, v. d. s. 
gran. ppt. appearing when the ammoniacal sol. of the acid is boiled 
w. CaCl,! ZnA, v. d. s. eryst. ppt.—Does not give Test 304. 


106 168 I, 3, 3-lrimethylcyclohexene(1)carbonic(2) Ac., C,,H,,0,.—B. p. 138° 
(11 mm.).—Ndl. fr. h. aq.—Unsat. 
106-7 148 | + Atropic Ac., CH,:CPh.CO,H.—B. p. 267° d.—Monoclin. tbl. s. in 692 


pt. aq. at 19°; s. CS,—Oxid. by CrO, to benzoic ac. (cf. Tests 
702 and 312)!—NaA sol. gives no ppt. w. MnCl,. (dif. fr. cin- 
namic #¢c.).—CaA,+5H,0O s. in 43 pt. aq. at 18°.—Gives Test 304! 


106-7 152 | m-Methoxybenzoic Ac., MeO.C,H,.CO,H.—Ndl. sbl. undec.—E. s. alc., 
eth., or h. aq.—Dist. of Cad, gives phenol (Test 414). 
107-8 212 | m-Benzylbenzoic Ac., Ph.CH,.C,H,.CO,H.—Nadl. fr. aq.; d.s. c. aq.; 


e. s. ale. or eth.—CrO, mixt. oxid. to m-benzoylbenzoic ac.— 
BaA,+4H,0, s. aq.; AgA, ppt., d.s, h. aq. 


108 228 | Phenylethermandelic Ac., Ph.HC(OPh).CO,H.—Ndl. fr. h. aq., v. d. s. 
c. aq.—Oxid. by h. dil. HNO, to benzaldehyde and picric acid. | 
108-5 168 | + Dehydracetic Ac. (Methylacetopyronon), C,H.O,.—B. p. 269-9° ¢.— | 


S. in 100 pt. aq. at 6°; e. s. h. aq., ale. or eth.—1 drop 10% FeCl, 
gives yellow or orange (YO-OY) ppt. in aqueous solution !—Sol. in 
NaOH pale yellow.—Boil w. conc. NaOH and test distillate for 
acetone (Test 711).—Evaporation of the sol. in v. conc. ammonia 
gives an amide, m. p. abt. 200°. 


es 











Melting-point 
(G.°). 
108-9 
109 


109-5 


110 
110-11 
110-5 


112 


112 
112-3 
112-3 

112-5d. 


113 


114 


115 


115 
115 


115 


115 
116 
116-5 


ws 
118 








GENUS @ le Dive Ames ECT, 2: 59 


(ORDER I, SUBORDER I.) 





Neut. [SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 


Equiv. 


126 


268 


160 


106 


198 


136 


122° 


194 


150 


166 


192 


214 


212 


164 


288 
162 


178 


226 


178 


164 


180 





in 50 parts of cold water. 


2, 5-Methylpyromucic Ac., C,H,O(Me).CO,H.—Ndl. d. s.c.aq.; v.s. h. 


aq.; e. s. eth.—Sbl easily.—BaA,, octahedra, v. s. c. agq— Warmed 
w. conc. H,SO,-+ trace of isatin gives chrome-green color! 

Dibenzoylacetic Ac., (Ph.CO)..CH.CO,H.—D. s. aq.; e. s. eth.—Ale. sol. 
gives reddish color w. FeCl,. Boiled w. dil. H,SO, gives benzoic 
acid and acetophenone (Tests 312 and 712). 

Methylphenylpropiolic Ac., Me.C,H,.C : C.CO,H.—Gives Test 304.—Ag 
salt explosive ppt. 

Ethyl Isocarbopyrotritarate, C,,H,,.O,.—Ndl. fr. h. aq.; v.d.s. c. aq.; 
e. s. alc. or eth.; e. s. NaOH, Na,CO, or ammonia, but reppt’d by 
CO,.—Ale. sol. blue w. FeCl,! Reduces Ag or Cu salts in the cold. 

o-Phenylbenzoic Ac., Ph.C,H,.CO,H.—B. p. 343°.—Ndl. d.s. h.aq.; e. 
s. h. ale-—UaA,+2H,0, d. s. aq.; ignited w. CaO gives diphenyl, 
etc.—Fuming HNO, at 0° gives nitro deriv., s. alc., m. p. 221°. 

m-Toluic Ac., Me.C,H,.CO,H.—B. p. 263°.—Pr. fr. h. aq. s. in 60 pt. aq. 
at 100°, e. s. alc. or eth.—Oxid. by CrO, ‘mixt. to isophthalic ac. 
(Tests 905-2 and 318). 

Brassylic Ac., CO,H.(CH,),,.CO,H.—100 pt.'aq. at 24° dissolve 0.74 
pt.; e. s. alc. or eth—CaA+H,O, pulv. ppt. 

Benzoyllactic Ac., Me.CH(C,H,0,).CO,H.—Cryst. s. alc. or eth., and in 
400 pt. c. aq.—Boiled w. dil. HCl gives benzoic ac. (Test 312) and 
lactic ac. 

p-Ethylbenzoic Ac., Et.C,H,.CO,H.—Lft. s. h. aq.; e. s. alc. or eth.— 
BaA,+2H,0, s. in 45 pt. c. aq.—Oxid. to terephthalic ac. (Test 905 
and 318). 

Phenoxypropionic Ac., Me.CH(OPh).CO,H.—V. d.s. c. aq.; e. s. h. aq: 
e. s. eth.—CaA,+2H,0, v. d.s. ale.; AgA, small ndl. blackened by 
light. 

Ethylbenzoylacetic Ac., Ph.CO.CHEt.CO,H.—Nadl. fr. dil. alc.; e.s. ale: 
or eth.—Boiling w. conc. alc. KOH gives benzoic ac. (Test 312) 
and butyric ac !—Oxime m. p. 89°-90°. 

Phenylethersalicylic Ac., o-PhO.C,H,.CO,H.—B. p. 355° d.—Lft. fr. 
dil. ale.; v.s. alc. oreth. NH,A, m. p. 180°. 

o-Benzylbenzoic Ac., Ph.CH,.C,H,.CO,H.—Sbl. in ndl.—D. s. ¢. aq.; 
e. s. eth.Warmed w. conc. H,SO, gives anthranol.—BaA,+ 
54H,0, s. aq. 

o-Acetophenonecarbonic Ac., Me.CO.C,H,.CO,H.—Cryst. s. cone. H,SO,. 
Sweet taste.—With alc. NH, at 100° gives comp., m. p. 204°. 
Sol. in conc. H,SO, on standing forms isomethylenephtalid, m. p. 
es 

Dioxypalmitic Ac., C,,H;,0,.—Lft. s. alc. or eth. 

m-Methylcinnamic Ac., Me.C,H,.CH:CH.CO,H.—Silky ndl. fr. h. aq.; 
e. s. eth. or bz.—FeCl, gives egg-yellow ppt. w. NH, salt.—Gives 
Test 304. 

m-Methoxycinnamic Ac., MeO.C,H,.CH: CH.CO,H.—S. h. aq.; e.s. eth. 
—Gives Test 304. 

p-Phenyltolylacetic Ac., C/H;.CHPh.CO,H.—Lft. fr. aq.; v. d.s. ¢. aq.; 
s. h. aq.; e. s. ale. or eth.—Oxid. by CrO; to p-phenyltolylketone, 
ete.—CaA,+H,0, d.s. h. aq. 

f-Benzoylpropionic Ac., Ph.CO.(CH,),.CO,H.—E. s. aq. at 70° 
Heated above m. p. turns orange-yellow. PbA,+2H,0O, ndl., d.s. 
c., e. Ss. h. aq. 

Cuminic Ac., p-Me,.CH.C,H,.CO,H.—Triclin. cryst. v. d.s.c. aq.; e. 8. 
eth.—BaA,, lft. s. in 100 pt. aq. at 20°.—Oxid. gives terephthalic 
ac. (cf. Tests 905-1 and 318). 

Pyromeconic Ac., C;H,0;.—Cf. Phenols. FeCl; gives cherry-red color! 

Salicylic Ac. Acetate, o-C,H,0,.C,H,.CO,H.—Fine ndl. fr. h. aq. 
FeCl, gives violet color w. aq. sol. !—Saponification by hot alkalies 
gives acetic and salicylic acids! (cf. Tests V, 311 and 319). 

















60 GENUS III, DIV. A, SECT. 2. 


(ORDER I, SUBORDER I.) 





Melting-point Neut. |SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 
cCGeS) 


%) Equiv. in 50 parts of cold water. 
119-6 261 t+ Succinic Anhyd., C,H,O,.0.—(For behavior on titration ef. remark 


on page 37.—Long ndl. fr. alc.; v. d. s. eth.—Test 307 gives ac. 
s. aq., m. p. 185° (Test 320). 
120 152 o-Oxymethylbenzoic Ac., HO.CH,.C,H,.CO,H.—Nadl. s. in 0-428 pt. aq. 


at 20°; s. eth.—In melting or on prolonged standing w. aq. gives 
phthalid, m. p. 73°.—Salts all soluble. 


abt. 120 Fellic Ac., C,,;H,,0,—(In human gall.)—Ndl. fr. dil. ale.; i. aq.; s. 
ale. or eth.—Taste bitter.—Opt. act.—BaA,+4H,0, s. in abt. 800 
pt. c. or h. aq.—Color reac. w. sugar and H,SO, (cf. H. 11. 274). 


d.120 264 | Santonic Ac., C,,H,,0,—\Cryst. gradually turn yellow.—D. s. c. aq.; 
e. s. alc.; d. s. eth.—Fusion on boiling w. aq. gives aq. and san- 
tonin. Opt. active.—Pb.A, (at 100°) ppt. 

120 or 127 192 | p-Toluyl-@-Propionic Ac., C;H,.CO.C,H,.CO,H.—Tbl. fr. Igr., e. s. h. 
aq., alc., or eth.—Turns red above m. p.—AgaA ndl. 

121 -2c. 122 | + Benzoic Ac., Ph.CO,H.—B. p. 249-2° c.—Monoclin. lft. or ndl.— 
Sbl. easily, vapor producing coughing.—S. in 344-8 pt. aq. at 20°, 
or in 17 pt. at 100°; at 15° s. in 2-14 pt. abs. alc., or in 3-19 pt. 
eth.— Apply Test 312! 


ey, 216 | Diisoamyloxalic Ac., (C;H,,),.COH.CO,H.—Silky fibres, s. eth.—Sbl.— 
BaA,, d. 8. c. aq. 

122 164 Cetylmalonic Ac., Me.(CH,),,.CH.(CO.H),.—Rhomb. tbl. d. s. c. ale.: 
e. s. eth.-alc.—BaA cryst. ppt.; Ag,A powd. ppt.—Gives Test 302. 

123 194 | o-Thymotic Ac., HO.C,H,(Me)(Pr).CO,H.—V. d.s. h. aq.; e. s. eth.— 
Blue color w. FeCl. ! 

123 139 | n-Dodecanedicarbonic Ac., CO,H.(CH,),..CO,.H.—Lft. mod. s. c. alc. or 
eth. 

124-5 324 | Lichen-stearic Ac., C,,H;,0,.CO,H.—Pearly plates, i. aq.; e. s. h. bz. 

or CHCl,.--Not attacked by Br or permanganate.—NH,A, pr. fr. 


h. aq. (m. p. 106°). 


125 161 | m-Tolylpropionic Ac., Me.C,H,.C,H,.CO,H.—Ndl. fr. h. aq—Oxid. by 
Test 905-1 gives isophthalic Ac. (Test 318-2). 
125 204 Benzallevulinic Ac., Ph.CH:C(CO.Me).CH,.CO,H.—Cryst. fr. CHCl. 


S. in conc. H,SO, w. red color !—After boiling w. conc. KOH gives 
iodoform reac. w. I. (Test 801). 








125 179 | a-Dihydronaphthoic Ac., C,,H,,0,.—S. in 3215 pt. c. aq.—Br addition- | 
product m. p. 152°. 
125-7 Fluorescine, C,,H,,0,.CO,H.—Ndl. s. Ac. or eth—Gentle oxid. gives | 
fluorescein ! ; 
126 150 1, 3-Dimethylbenzoic(4) Ac., Me,.C,H,.CO,H.—Sbl.—B. p. 268°.—D. 
s. h. aq.; e. s. h. ale—CaA,+2H,0, and BaA,+2H,0, e. s. aq. 
127 164 I, 2, 4-Trimethylbenzoic (6) Ac., Me,.C,H,.CO.H.—Thbl., fr. lgr., v. d. s. 
c. aq.; s. h. aq.; v.s. ale. or eth.—Volat. w. steam. Distils un- 
decomposed.—Ignited w. CaO gives pseudocumene. 
127 178 | m-Isobutylbenzoic Ac., C,H,.C,H,.CO,H.—Nadl. fr. lgr —Amide, ndl. fr. 
adi, My plod 
127 180 mmnepere es Ac., C,H,0,.C,H,.CO,H.—Cryst. s. h. aq.; e. s. alc, 
or eth. 
127-8 166 | [+] Tropic Ac., Ph.CH(CH,OH).CO,H.—Hard pr. fr. eth. 
128 144 | Lactide, C,H,O,.—B. p. 255°.—Monoclin. tbl. fr. h. abs. ale., alm, i. ¢. 





aq.; ve d. s. ale.-—Boil w. aq., and apply Test 302 for lactic ace. 
to the cold solution.—Dry NH, gas gives lactamide, s. aq., and 
alo. o Mop4y 

128 158 | Oxyroccellic Ac., C,,H;,0,.—Lft. of greasy feel, e. s. eth. or CHCl,.— 
At 160° gives anhyd. m. p. 82°.—Ag,A floc. ppt. 





Melting-point 
(.°); 





128 


128-9 


128-9d. 


128-9 
128-30 
128-5 
130 
130-5 
130-40d. 


131 


133-3 :-5 


133-4 


133-5 


134-5 


135 


135 





Neut. 
Equiv. 


74 


166 


196 


170 


101 


a eee 





GENU See Diy swe CG dee 2: 61 


(ORDER I, SUBORDER 1.) 





SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 
in 50 parts of cold water. 





} Phthalic Anhyd., o-C,H,.(CO),.0.—B. p. 284-5c., subliming in fine 
long ndl.—Alm. i. ¢. aq.; s. h. aq. or c. ale-—Mix a few mgrms. w. 
an equal quantity of either phenol or resorcin; barely moisten w. 
conc. H,SO, and fuse according to Test 402. The fused mass dis- 
solves in dil. alkalies, in the first case with the deep red color of 
phenolphthalein, or, in the second case, with the strong green 
fluorescence characteristic of fluorescein. 


p-Hydrocumaric Ac., HO.C,H,.(CH,)..CO,H.—Monoclin. cryst., e. s. h. 
aq., alc., or eth.—Cold sat. aq. sol. becomes blue-gray w. 1 drop 
FeCl, sol—Reacts like tyrosin w. HgN,O,.—No ppt. w. PU.Ac, or 
w. BaCl, —-ZnA,+2H,O, s 130 pt. c. aq. 


Camphocarbonic Ac., C,,H,,0,.—D.s. aq.; e.s.eth. Fusion gives cam- 
phor and CO, (Test 715)! FeCl, gradually added to alc. sol. gives 
first a dark blue and finally a dark green !—Easily oxid.—Br sub- 
stitutes easily, giving ac. m. p. 109°. 


Pinonic Ac., C,H,,0,.—Cryst. fr. CHCl,; d.s.c. aq.; v.d.s, lgr.—B. p. 
(17 mm.), 187°-93°. 


Glycollic Anhyd., C,H,0,.— Powder i. c. aq., ale., or eth.; s. h. aq. giving 
glycollic ac.—Heated above m. p. gives glycollide (m. p. 220°). 


{-Methoxyisocrotonic Ac., Me.C(OMe):CH.CO,H.—S alc. or eth. 
Gives Test 304. 


Hydrindoncarbonic Ac., C,H,.C,H;.CO,H.—Ndl. s. in 120 pt. aq. at 
100°.—BaA, v- s. aq.—Oxid by alk. KMnO,.—Br substitutes cold. 

Cinnamic Anhyd., (C,H,0O),0.—I. aq.; v. d. s.c. ale.—Cryst. powd. 
Test 307 gives acid of Test 313. 

Acetophenoneacetacetic Ac., (C,H,0)(C,H,O).CH.CO,H.—Heai gives 
acetophenoneacetone and CQ). 

a-Naphthylacetic’ Ac., C,,H,.CH,.CO,H.—E. s. h. aq.; e. s. eth.— 
Ignition w. CaO gives a-methylnaphthalin. 

1, 4-Dimethylbenzoic(2) Ac., Me,.C,H;.CO,H. — B. p. 268° (th. 1.) — 
Ndl. v. d. s. h. aq.; v. s. ale-—CaA,+2H,O, mod. s. aq.—Amide, 
nal. dis. bh. ag.sm. p. 186°. 

a-Ethylnaphthoic Ac., Et.C,,H,.CO,H. 

Roccellic Ac., C,,H;,0,—(In certain alge.)—Cryst., i. h. aq.; e.s. 
ale. or eth.; s. Na,CO;—Swells up in cone, KOH, dissolving after 
dilution w. aq.—Ag,A, i. aq ; CaA, 1. aq. 

{+ Cinnamic Ac., Ph.CH:CH.CO,H.—B. p. 300° without dec., but does 
not sublime.—Monoclin. pr. fr. ale-—Odor faintly aromatic.— 
S in 1000 pt. aq. at 20°; in 4.3 pt. alc. at 20°; v.s eth.; s. CHCL,; 
d. s. CS, —Warmed w. CrO, mixt oxid. easily giving strong odor 
of benzaldehyde.—Identify by Test 313! 

Sebacic Ac., CO,H.(CH,),.CO,H.—B. p 243-5° (15 mm.).—Thin Ift. s. 
in 1000 pt. aq. at 17°, or in 50 pt. at 100°; e. s. alc. or eth.—Stable 
toward CrO, mixture —CaA, ppt —Ignition w. BaO gives octane. 
Oxid. w. dil. HNO, gives adipic, glutaric, and succinic acids. 

6-Naphthoic Anhyd., (C,,H,O),0.—D. s. c. eth.; s. h. eth. or h. bz. 
Obtain acid of m. p. 184° c- by Test 307. 

Cis- (iso) Campholitic Ac., C,H,,0,.—B. p. 255°-6°.—Pr. fr. dil. ale.— 
Odor camphor-like —S. 5000 pt. c aq.; e. s. ale.—Unsat.— 
CaA, + 34H,O, ndl.,e.s.aq.; ZnA,,s. eth.; i aq. 

Sorbic Ac., Me.CH: CH.CH:CH.CO,H.—B. p. w. dec. 228°.—Long ndl. 
fr h. aq.; e. s. ale. or eth.—BaA,, silvery scales scarcely more s. 
in h. than in c. aq.—Gives Test 304. 

(@)o-Ethoxycinnamic Ac., C,,H,,0;.—Ndl. fr. h. aq.—CaA,+2H,0, 
v. d. s. c. aq.—Gives Test 304. 


Methylatropic Ac., Me.CH:CPh.CO,H.—Gives Test 304. 











2 GENUS III, DIV. A, SECT. 2; 


(ORDER I, SUBORDER I.) 





Melting-point Neut. |SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 
(9%: Equiv. in 50 parts of cold water. 
135 140 2, 5-Dimethylfurfuranecarbonic (Uvic) Ac., (Me,).C,HO.CO,H.—Ndl. 


s.400 pt. h. aq.; e. s. ale. or eth—Warmed w. 2 drops fuming 
HNO, and then treated w. 6 drops conc. H,SO, gives cherry-red 
color.— Br substitutes very easily.—With aq. at 160° gives acetyl- 
acetone.—BaA,+4H,0O, ndl. d. s. c. aq.; ZnA,+8H,O (charac. 
cryst. aggregates) more s. c. than h. 

136-7 146 | } Phenylpropiolic Ac., Ph.C:C.CO,H.—V. long hair-like ndl. fr. h. 
aq.—kKE. s. alc. or eth.—Melts under h. aq. at 80°.—Boiled w. Zn 
dust in glacial Ac. gives cinnamic ac. (Test 313).—Reduced by Na 
amalgam to hydrocinnamic ac.—Salts unstable in h. sol.—Gives 


Test 30+. 
136-5 316 | Dioxystearic Ac. (from oleic ac.), C,,H,,0,—Lft. e. s. h. ale—BaA,, 
gran. ppt., 1. aq. or alc. 
137 166 | m-Ethoxybenzoic Ac., EtO.C,H,.CO,H.—Ndl. d. s. h. aq.; s. ale. or 
eth.— BaA,, e. s. h. aq. 
137-5 121 | @-Ethoxyisocrotonic Ac., MeC(OEt):CH.CO,H.—Pr. s. alc. or eth.— 
Boiled w. dil. H,SO, gives acetone (Test 711). 
139 234 | p-Octylbenzoic Ac., C.H,,.C,H,.CO,H.—Lft. fr. h. ale.; v.d.s. h. aq.— 
Ag.A bulky ppt. 
140 164 | p-Propylbenzoic Ac., Pr.C,H,.CO,H.—Lft. fr. h. aq. e. s. ale. or eth.— 
Oxid. by KMnO, to terephthalic ac. (Tests 925 and 318). 
140 87 | Suberic Ac., CO,H.(CH,),.CO,H.—B. p. abt. 300° without dec.—Ndl. 


or tbl. v. d. s. eth.; alm. i. CHClI,; s. in 704 pt. aq. at 15-5°.— 
CaA+H,0O, s. in 161 pts. aq. at 14°.—BaA, s. c. aq., less s. h. aq. 
Ignition w. BaO gives hexane. 


140-1 87 | a, s-Dimethyladipic Ac., CO,H.CHMe.(CH,),.CHMe.CO,H.—B. p. 321°. 
—D. s. eth. . 
141 332 | Trioxystearic Ac., C,,H;.(OH),.CO,H.—Ndl. fr. h. aq. d. s. eth. 
141 138 | Furfuracrylic Ac., C,H,0O.CH:HC.CO,H.—B. p. 255°-65° d.—Thin 


ndl. s. 500 pt. c. aq.; e. s. eth. or alc-—S. in cone. HCl w. green 
color !—Ba salt v. s. aq. or alc.—Gives Test 304. 


141-3 316 | Dioxystearic Ac., C,,H;,0, (fr. Castor-oil).—I. eth.; d. s. c. ale-—HI 
reduction gives stearic ac. 
141-3 180 | 4-Methoethylphenol(3)carbonic(1) Ac., C,,H,,0,—Boils w. decomp. 


—Ndl. fr. aq., v. d. s. c. aq.; s. h. aq.; v. s. alc. or eth.—Not ppt’d 
in dil. sol. by Pb.Ac,; BaA,, e. s. aq.—Long fusion w. KOH gives 
m-oxybenzoi¢e ac. 
142d. 160 | Agaricic Ac., C,,H,,0,—Silvery lft. fr. 30% ale. (Cryst. w. 1H,O 
which is lost at 100°; loses more aq. in melting.)—Gelatinizes w. 
boiling aq., dissolves, and cryst. out on cooling.—D. s. alc. or eth.— 
(Obtained fr. Polyporus officinalis.).—BaA, amorph. ppt.; Ag,A 
(at 90°) gelat. ppt. 
142-3 87 + Hydrochelidonic Ac., CO.(CH,.CH,.CO,H),.—Rhomb. tbl. d. s. aq. 
or eth.; i. bz.; s. ale-—Above m. p. gives anhydride (lft. fr. dil. 
alc., m. p. 75°). Oxid. by HNO, or alk. KMnOQO, to oxalic and 
succinic ac. (Test 320).—BaA+2H,0, e. s. lit.; ZnA+2H,0, 
charac, 6-sided 1. lft. 


142-4d. 204 Benzoyltetramethylenecarbonic Ac., C,,H,,0,.—Pr. fr. eth. v. d. s. c. 
aq.; e. s. ale. or eth.—AgaA cryst. ppt. 
144 150 1, 2-Dimethylbenzoic(3) Ac., Me,.C,H;.CO,H.—Glassy pr. fr. ale. — 
V. d. s. h. aq.—CaA,+H,O, mod. s. c. aq.; ignited w. CaO gives 
o-xylene Test 921. 
144d. 90 perpen Cl 3) <Ac., C,H;(Me)(CO.H),.— Anhyd. melts at 
09°-10°. 
145 163 | a-Naphthoic Anhyd., (C,,H;0),0.—V. s. alc.; s. eth. or bz.—Test 307 
gives a-Naphthoic ac., m. p. 160°. 
145-6 166 | p-Methylmandelic Ac., Me.C,H,.CHOH.CO,H.—Thbl. fr. h. aq.—Gives 


Test 302 w. FeCl,. 





= _———— 








Melting-point 
CC): 


146 


146 
147-8 


148 


148 sbl. 


149-50 


150 


150 


150 
151 


151-2 


152 


153c. 


153-4 


Neut. 
Equiv. 


240 


122 


212 


180 


164 


210 


228 


148 


152 


254 


164 


73 | 


288 


168 
212 
302 
141 


164 


GENUSSILE DIV AS SEC Tee 2. 63 


(ORDER I, SUBORDER I.) 


SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 


in 50 parts of cold water. 


p-Toluyl-o-benzoic Ac., Me.C,H,.CO.C,H,CO,H.—V. d.s. h. aq.; the 


milky ppt. that separates on cooling gives lft. containing aq. of 
cryst.—E. s. ale. or eth.—Dec. on dist.—BaA,+4H,0., d.s. aq.; 
Pb.A,, s. eth. NaA melted w. 5-6 pts. KOH gives benzoic ac.+ 
p-toluic ac. 

Acetcumaric Ac., C,H,0,.C,H,.C,H,.CO,H.—Ndl. e. s. h. aq.—Heated 
gives coumarin (charac. odor of ‘‘ sweet grass’) and acetic ac. 

Diisoamylmalonic Ac., (C,H,,),..C.(CO,H),.—E. s. alc. or eth.; v. d. s. 
aq.—At 175° gives CO, and disoamylacetic ac. (Test 303). 

Diphenylacetic Ac., Ph,.CH.CO,H.—Ndl. e.s. h.aq., ale, oreth. CrO, 
mixt. (cf. Test 905-2) slowly oxidizes to benzophenone (Test 714), 
—Ba salt ignited w. CaCO gives diphenylmethane. 

I, 2, 4-Trimethylphenol(6)-Methanoic(5) Ac., C,,H,,0;—Ndl. fr. dil. 
alc.; v. d.s. h. aq.—FeCl, gives transient blue w. dil. ale. sol_— 
CaA,+2H,0, glassy pr. s. c. aq. 

I, 2, 4-Trimethylbenzoic(5) Ac., Me..C,H,.CO,H.—Long ndl. fr. bz.; 
d. s. h. aq.; v. s. eth—The amide melts at 200°-201°. 

t Opianic Ac., C,,H,,0;.—Thin pr. s. in 400 pt. c. or 60 pt. h. aq.; s. ale. 
or eth.—Mix on a porcelain crucible cover 3 mgr. of the acid, an 
equal bulk of phenol, and 3 drops cone. sulphuric acid. A strong 
red-orange color (RO-O) is immediately produced.—BaA,+ 
2H,0, pr. e. s. aq.—Reduction w. Na amalgam gives meconin.— 
[Does not give Generic Test I.] 

7 Benzilic Ac., Ph,.COH.CO,H.—Monoclin. ndl., e. s. h. aq.—Taste 
slightly bitter—1 mgr. dissolved in 3 drops cone. H,SO, on 
a crucible cover at once gives an intense orange-red [OR.} 
coloration which soon becomes red-violet [RVTI] about the edges, 
—Gives Test 302.—Oxid. by CrO; mixt.—BaA,. e. s. melting under 
h. aq. 

Homococaic Ac., C,H,O,.—Ndl. e. s. alc. or eth. Fuming HNO, gives 
nitro compound, m. p. 226°. 

4-Oxy-m-toluic Ac., HO.C,H,(Me).CO,H.—Nadl. fr. aq.; d.s. ¢. aq.; 
v. s. ale. or eth.—Volat. w. st.—FeCl; gives intense blue violet 
color! BaA,+2H,0, lft. v. s. aq. 

a-Ditolylpropionic Ac., (C;H,),.CMe.CO.H.—Cryst. fr. alc. or eth.; e. 
s. eth. or h. alc.—Volat. without dec.—Heated w. CaO gives 
p-ditolyethane.—BaA, pulv. ppt. 

I, 3, 5-lrimethylbenzoic Ac., Me;.C,H,.CO,H.—E. s. alc. or eth.; v. d. 
s. aq.—Dist. undec.—Ignition w. CaO. gives mesitylene (cf. Test 
914).—M. p. of amide, 158°. 

+ Adipic Ac., CO,H.(CH,),.CO,H.—Boils without dec.—Flat ndl. s. in 
69 pt. aq. at 15°; v.d.s. eth.; e. s. ale—May be cryst. without 
dec. fr. h. conc. HNO.—CaA + H,O, d.s.h. orc. aq.; BaA, e. 8. ¢. 
aq., lesss. h.; Zn.A cryst. ppt. less s. in h. than in c. aq. 

Abietic Ac., C,,H,,0,.—(Principal constituent of Rosin.)—Cryst. fr. alc., 
easily s. alc., eth., or CS,.—Salts amorph.—Addition of a little 
acetic anhyd. and a drop of H,SO, to a CHCl, sol. gives a purple 
color, quickly changing to intense blue. 

p-Methoxysalicylic Ac., HO.C,H,(OMe).CO,H.—S. in 40 pt. h. aq.; 
e. s. alc. or eth.—FeCl, gives sol. intense red-violet color. 

p-Benzylbenzoic Ac., Ph.CH,.C,H,.CO,H.—Nadl. fr. h. aq.; e.s. eth.— 
CaA,, ppt. CrO, gives p-Benzoylbenzoic ac. 

p-Tolyldiphenylmethanecarbonic Ac., Me.C,H,.CHPh.C;H,.CO,H.— 
Nal? fr ale. 

Photosantonic Ac., C,;H,,0; (dried at 100°).—Pr. fr. alc.; v. d.s. ¢. aq.; 
e. s. alc. or eth.— Ag,A +3H,O, curdy ppt. 

Phenylpyruvic Ac., Ph.CH,.CO.CO,H.—Lft. fr. CHCl,; v. d.s. h. aq.; 
e.s. alc. or eth.—Ale. sol. gives intense blue-green color w. FeCl;.— 
Gives off CO, in melting —Na amalgam gives phenyllactic ac. 











64 





Melting-point 
(Oe). 
155 
155 


d. abt. 155 


155-6 


156-7 
156-7 
156-7 (x. h.) 
((s.h.)124-8d.) 
157-8 
158 


158e. 


159 
159 
159-60 
159-5 


160 
160-1 


160-1 


161 


|| 2 ja STSSTSTSGS S| T™O™ oo . 


Neut. 
Equiv. 


125 


74 





GENUS Mil, DIV. A, WSECTS2: 


(ORDER I, SUBORDER I.) 


SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 
in 50 parts of cold water. 


Stilbenedicarbonic Anhyd., C,,H,,0,—B. p. 236° (15 mm.).—Find 


ndl.—Sbl. undec.—l. ¢., v. d.s. h.aq.; 1. Na,CO,.—Is oxid. in cold 
by KMnO, to benzoic ac. (‘Test 312).—[The free ac. is unknown ] 

Isodehydracetic Ac., C,H,O,.—Ndl. fr. c. alc.; d.s.c¢., v.38, h. aq.— 
At 200°-245° loses CO,.—Warmed w. Ba(OH), splits to CO,, 
mesitvl oxide and oxymesitenecarbonic ac. 

Dioxymaleic Ac., CO,H.C(OH) : C(OH).CO,H.—Pearly Ift., d. s. c. aq. 
or eth.; e. s. alc—Heated w. aq. dec. to CO, and glycolaldehyde.— 
FeCl, gives blackish color, becoming violet upon addition of KOH. 
—BaA+2H,0 (dried 1. v.), cryst. ppt. 

p-Oxyisopropylbenzoic Ac., Me,.C(OH).C,H,.CO,H.—Pr. fr. h. aq., e. s. 
ale. or eth.—Oxid. by CrO,; mixt. (Test 905-2) gives terephthalic 
ac. (Test 318).—BaA,+H,0O, v. s. aq.; AgA, tbl. d.s. h. aq. 

Dibenzylglycollic Ac., (PhCH,),.C(OH).CO,H.—4-sided pr. fr. ale.; e. 
s. eth. Boiled w. KOH (G. 1-2-1-3) gives oxalic ac. and toluene. 

Isatronic Ac., C,,H,,0,.—Lft. fr. dil. ale-—CaA,, volum. ppt., d.s. h. aq. 

2-Oxynaphthoic(1) Ac., HO.C,,H,.CO,H.—V. s. ale.—Alc. sol. gives 
blue color w.  FeCl,.—Fusion or long boiling w. aq. gives CO, and 
$-naphthol (Test 413). BaA. ppt. (dif. fr. salicylic ac.). 

a-Trimellitic Anhyd., C,H,O;.—Cryst. d. s. c., e. s. h. aq.—M. p. of 
trimellitic ac. (Test 307), 216° d. 

p-Isoamylbenzoic Ac., Me,.CH.(CH,),.C,H,.CO,H.—Ndl. fr. h. aq.— 
E. s. alc. or eth.—Oxid. to terephthalic ac. (Test 905-1). 

1 Salicylic Ac., o-HO.C,H,.CO,H.—Ndl. fr. h. aq., s. in 370 pt. aq. 
at 20°, v.s. ale. or eth.; e. s. CHCl,—Sol. in aq. (1:10,000) gives 
purple coloration (RV-VR) w. 1 drop 10% IeCl; sol. (cf. Test 
401)!—Apply Test 319! 

Stilbene-o-carbonic Ac., Ph.CH:CH.C,H,.CO,H.—E. s. aic. or CHCl,.— 
Gives Test 304. 

Diphenyllactic Ac., Ph..CH.CHOH.CO,H.—Nadl. fr. h. aq., e. s. alc. 
or eth. 

trans-Pentamethylene-1, 2-dicarbonic Ac., C,H,.(CO,H),.—E. s. h. 
aq.—CaCl, hoiled w. (NH,),A. sol. gives ppt. 

p-Phenoxybenzoic Ac., PhO.C,H,.CO,H.—Coffin-shaped pr. fr. CHCl. 
—F. s. ale. or eth.—Heated w. baryta gives phenylether. 

a-Naphthoic Ac., C,,H,CO,H.—Ndl. e. s. h. ale; v. d.) 3) ages 
CaA,+2H,0, nd!. s. in 93 pt. aq. at 15°.—-Ignition w. CaO gives 
naphthalene (Test 915). 

m-Phenylbenzoic Ac., Ph.C,H,.CO,H.—Lft. e. s. ale. or eth—BaA,+ 
34H,O, ndl. e. s. aq. (dif. fr. para ac.).—Oxid. by Test 905-1 
gives isophthalic ac. (Test 318-2). 

p-Propenylbenzoic Ac., CH,:CMe.C,H,.CO,H.—Lft. d. s. h. aq.; v. s. 
ale. or eth.—BaA,+ H.,O, lft. v. s. aq.—Gives Test 304. 

Hemipinic Ac., (MeO)..C,H,.C,OH.—M. p. varies much according to 
method of heating. Cryst. fr. h. aq. w. xH,O.—TleCl, gives 
orange color w. aq. sol—W. KOH at 220° gives protocatechuic 
ac.—NH,A+H,0 at 110° gives hemipinimide, ndl. fr. alc., m. p. 
228°-30°, alc. sol. fluorescing blue. 

@-Dihydronaphthoic Ac. (stable form), C,,H,,0,.—Lft. i. ¢. aq.; 
e. s. ale. or eth.—Easily oxid. to phthalic ac. (Test 318) by KMnO,. 

p-Triphenylmethanecarbonic Ac., Ph,.CH.C,H,.CO,H. 

m-Benzoylbenzoic Ac., Ph.CO.C,H,.CO,H.—Shl. in lft.—E. s. ale. or 
cth.—Fusion w. KOH gives benzoic ac. (Test 312). 

o-Triphenylmethanecarbonic Ac., (C,H;),.CH.C,H,.CO,H.—I aq.; e. 
s. ale. or eth.—Ignition w. BaO,H, gives triphenylmethane.— 
Dissolve 1 pt. ac. in 3 pt. conc. H,SO,, ppt. sol. w. aq.; wash ppt. 
w. cold NaOH and recryst. fr. abs. ale. Phenylanthranol is 
formed, yellow. ndl,, m, p. 141°-4° d. 











Melting-point 
(Ce): 





162 


163 
163-4 
164 
164 
164 


164-5 
165 


165-6 
166 
167 

167-5 


168 


168-9 


168-9 


169 
169-70 


171 
171-2 
171-5-2-5 
172 
172 


172-3 


172-5-3 


173 


GENUS Ill, DIV. A, SECT. 2. 65 


(ORDER I, SUBORDER I.) 


SSS ah 


Neut. SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 


Equiv. 


226 


150 
152 
178 
250 


142 





in 50 parts of cold water. 


Diphenyleneglycollic Ac., C,,H,,O,.—(Dried at 80°.)—Cryst. w. 4H,0O. 
—V.d.s.c¢., e. s.h.aq.; s. ale. or eth—Warmed w. conc. H,SO, 
gives indigo-blue sol. !—CaA,+2H,0, d. s. c. aq. 

I, 2-Dimethylbenzoic (4) Ac., Me,.C,H,.CO,H.—Pr. fr. alc.; v. d. 
s. h. aq.—CaA,+2H,0 and BaA, e. s. aq. 

2-Oxy-m-toluic Ac., HO.C,H,(Me).CO,H.—Nadl. e. s. h. aq.—Intense 
violet. color w. FeCl,—CaA, ©. s. aq. 

p-Isobutylbenzoic Ac., Me,.CH.CH,.C,H,.CO,H.—Sbl. in ndl.; e. s, 
ale. or bz.—CaA, tbl. d. 6. ¢. aq.—M. p. of amide 171°, ndl. fr. aq. 

Atronic Ac., C,,H,,0,.—Alm. i. h. aq.; e s. ale-—CaA,+6H,0, ppt 
d. s. h. aqg.—Unsat. 

Diphenylglutaric Ac., CO,H.CH(Ph).CH,.(Ph)HC.CO,H.—Nadl. fr. h. 
ivi NPS ore ral aed Rep 

Ethylitaconic Ac., C,;H,,0,.—D. s. aq.—Unsat. (cf. Test 304). 

I, 2, 3, 4-Tetramethylbenzoic(5) Ac., Me,.C,H.CO,H.—Ndl. fr. ale.— 
BaA, e. s. alc. or aq. 

o-Hydrocinnamocarbonic Ac., CO,H.C,H,.(CH,),CO,H.—Ndl. e. s. h. 
aq.—BaA, v. s. aq. 

Dimethylbenzoic(5) Ac., Me,.C,H,.CO,H.— Pr. v d.s. h. aq.; e. 8, 
ale.—CaA, ignited w. CaO gives p-xylene.—M. p. of amide 133°, 

Phenylsuccinic Ac., CO,H.CHPh.CH,.CO,H.—E. s. h. aq.—(NH,).A 
boiled w. CaCl, sol. gives pulv ppt. 

Prehnitilic Ac., Me,.C,H,.CO,H.—Glassy pr. fr. ale. ‘‘Somewhat s, 
in aq.” 

Methylphenol(3)-methanoic(2) Ac., HO.C,H,(Me).CO.H.—Ndl. fr. 
aq. SS. in 700 pt. c. aq.; e. s. h. aq.; e. 8. alc. or eth.—Aq. sol. 
gives intense blue-violet w. FeCl,;.—Ca salt v. e. s. aq. 

Ferulic Ac., MeO.C,H,OH.C,H,.CO,H.(3, 4, 1).—Ndl. s. h. aq— 
After long boiling reduces Fehling’s sol.—Floc. yellow. ppt. 
w. PbAc,. 

Cinchoic Ac., C-H,O,.—Tbl. e. s. h. aq.; d. s. eth—BaA+3H,0, 
silky ndl., d. s. aq. 

o-Methylcinnamic Ac., Me.C,H,.CH:CH.CO,H.—Ndl. fr. bz.—Unsat. 

s-Methylethylsuccinic Ac. (fumaroid), CO,H.CHMe.CHEt.CO,H ~ 
S. in 51 pt. aq. at 16°.—BaA + 5H.0, e. s. aq. 

p-Methoxycinnamic <Ac., Me0O.C,H,CH:CH.CO,H.—Ndl. s. ale.— 
Unsat. 

[+ and —]Isocamphoric Ac., C,,H,,0.—S. in abt. 300 pt. c. aq. 

Camphenylic Ac., C,,H,,0,—Opt. inact.—AgaA cryst. ppt. 

a-Phenylcinnamic Ac., Ph.CH:CPh.CO,H.—Nadl. e. s. alc. or eth— 
Unsat. ‘‘(Does not add Br).’’—Sbl. 

Oxytoluic Ac., Me.C,H,OH.CO,H(1, 4, 2).—Pr. e. s. h. aq.; v.s. ale. or 
eth.—Brown ppt. w. FeCl. 

Oxytoluic Ac., Me.C,H,OH.CO,H(1, 6, 3).—(Loses 4$H,O of cryst. at 
100°.) —Ndl.-e. s. h. aq., ale., oreth. CuA,+4H.0O, floc. ppt.; char- 
acteristic dark-green crystals fr. h. aq.—M. p. of methylester 67°. 

Ethylmesaconic Ac., C,H,,0,—Lft. d. s. ¢. aq.; e. s. h. aq., ale., or 
eth.—Ca salt separates in ndl. on heating c. sat. sol. 

Methyldiphenylacetic Ac., MeCPh,.CO,H.—B. p. a. 300°.—E. s. eth. 
or h. ale.—BaA,+2H,0O, cryst. ppt.—Oxid. by CrO, mixt. to 
benzophenone and benzoic ac. (Tests 714 and 312). 

Tetraoxystearic Ac., C,,H,.0,.(OH),—(Fr. oxid. of linoleic ac.) 
Silky ndl. or pr. fr. bz.—I. c. aq. or eth.; s. in 2000 pt. h. aq.; 
d. s. ale-—Alkaline KMnO, gives azelaic ac.—BaA,, floc. ppt. 

Ethyldiphenylacetic Ac., Et.CPh,.CO,H.—Lft. fr. dil. alc. 


66 GENUS III, DIV. A, SECT. 2. 


(ORDER I, SUBORDER I.) 





| 
Melting-point Neut. [SOLID ACIDS.—Colorless and generally not solub4s (ef. note, p. 38) 
cena i 


Equiv. in 50 parts of cold water. 


473-5 


174 


ér.h.)179-82d. 


180-1 


180: 7c. 


181 


276 


210 
108 


90 


170 


100 


144 


aie 





Naphthoyl-o-benzoic Ac., C,,H;.CO.C,H,.CO,H.—Pr. fr. dil. ale.—V. 


d. s. h. aq.—H,SO, gives naphthanthraquinont.—Ba salt, e. s. 
aq. or alc. 

Terebic Ac., C,H,,O,.—Large monoclin. cryst. fr. ale.; d.s. ¢. aq.— 
Not attacked bv fuming HNO,.—W. cone. BaO,H, sol. at 150° 
gives acetone (Test 711) and succinic ac. (Test 320)—Pb and 
Ag salts e. s. aq. 

Fluorenecarbonic (4) Ac., C,,H,,0,.—Crvyst. e. s. ale. or e6ls—M. p. of 
methyl ether 64°. 

1, 2-Naphthalenedicarbonic Ac., C,,H,.(CO,H),.—Cryst. s. h. aq. 
Fusion gives anhyd., m. p. 165°.—BaaA, d. s. ndl. 
Homophthalic Ac., CO,H.C,H,.CH,.CO,H.—Fusion w. soda lime gives 

toluene (cf. Test 918).-—BaA, e. s. aq. 

Camphoronic Anhyd., C,,H,.0,.—Alm. i. ec. ale., eth., or lgr.—s. in 
alkalies (forming camphoronic ac., e. s. aq.; m. p. 136°). 

Orsellinic Ac., Me.C,H,(OH),.(CO,H)(1, 3, 5, 4).—Cryst. w. 1H,O. E, 
s. ale. or eth.—Gives purple-violet color w. FeCl,—Boil w. aq. and 
test: sol. for orcine (cf. p. 95).—BaA,+2H,0 v. s. aq. 

p.-Toluic Ac., Me.C,H,.CO.H.—B. p. 275° c.—V. s. h. aq.; e. s. alc. or 
eth.—Oxid. to terephthalic ac. by Test 905-2.—The amide melts 
at 156°. Odor of methylester intense and agreeable; m. p. 32°. 

Oxytoluic Ac., C,H;(Me)(HO).CO,H(1, 3, 4).—Shl.—Nd1l. fr. h. aq.-- 
Gives intense violet color w. FeCl,! CaA,+3H,0O, e. s. aq. 

8-Triphenylpropionic Ac., Ph,.C.CH,.CO,H.—Pr. e. s. ale. or eth.— 
BaA,, ppt., d. s. h. aq. 

[+]Santonous Ac., C,,H,,O,—Ndl. d. s. c. aq.; e. s. eth. or Na,CO, 
sol.—MeA, m. p. 81°-84°. 

Oxymesitylenic Ac., Me,.C,H,(OH).CO.H(1, 3, 4, 5).—Ndl. d. s. h. aq.; 
e. s. eth.—Gives intense blue w. FeCl,! CaA,+2H,0, e. s. h. aq. 

I, 2, 4, 5-letramethylbenzoic Ac., Me,.C,H.CO,H.—Lft. v. s. ale-—Sbl. 
—M. p. of methylester 59°. 

m-Hemipinic Ac., C,H,.(CO,H),(MeO).(1, 2, 4, 5).—Sometimes cryst. 
w. 1 or 2 mols. H,O.—Pr. d. s. aq.—FeCl, gives orange-red ppt. in 
the aq. sol.! Fusion w. KOH gives protocatechuic ac. 

a, a-Methylphenylfuranecarbonic Ac., C,,H,,0;.—Sbl. in ndl—E. s, 
alc. or eth.; d.s. h. lgr.—Very easily oxid. to benzoic ac. (Test 312) 
by alkaline permanganate. KA-+aH,0 ndl. almost i. in x’s of 
alkali. 

+{+]Camphoric Ac., C,,H,,0,.—\ Cryst. s. in 160 pt. aq. at 12° or in 
11-12 pt. at 100°; v.s. alc., i. CS,—\ Heated in test-tube w. conc. 
H,SO, evolves CO, which burns w. pale-blue flame.—BaA + 44H,0, 
s.in 1 pt. aq.; PbA, i. ppt.—Na,A sol. boiled w. sol. of MnSO, gives 
ppt. which redissolves as sol. cools.—The properties of the [—]ac., 
except the optical ones, are like those of the [+ ] acid. 

Veratric Ac., (MeO),.C,H;.CO,H(3, 4, 1).—Cryst. w. 1H,O.—Sbl.—D. 
s. h. aq.; v.s. alc. or eth. Yellow color w. FeCl;—BaA,+6H,0, 
nd hds)c..d: 

I, 2, 4-Irimethylphenol(5)-carbonic(6) Ac., C,H.(Me),(OH)(CO,H).— 
Ndl. mod. s. eth.; d. s. other solvents.—Sbl.—Ale. sol. blue w. 
FeCl, !—Dist. gives CO, and pseudocumene (cf. Test 917). 

Methylphenol(6)-carbonic(2)-Ac., Me.C,H,(OH).CO,H.—Brown ppt. 
w. FeCl,.—Cf. Sect. 1. 

s-Diphenylsuccinic Ac., CO,H.(CH.Ph),.CO,H + H,O.—Solidifies after 
melting and fuses again at 220°. V.s. alc—BaA,+2H,0,v.d.s.¢. aq. 

G-or Iso-Naphthoic Ac., C,,H,;.CO,H.—B. p. a. 300°.—Silky ndl. v. d.s. 
h. aq. or c. lgr.; e. s. alc. or eth.—BaA, + 4H,0, ndl. s. in 1400 pt. 
aq at 15°. CaA,+3H,0Q, ndl. fr. h. aq.; s. in 1800 pt. aq. at 15°, 
—Methylester, m. p. 77°.—Test 905-1 gives trimellitic ac. 














GENUS III, DIV. A, SECT. 2. 67 


(ORDER I, SUBORDER I.) 





Melting-point Neut. |SOLID ACIDS.—Colorless and generallv not soluble (cf. note, p. 38) 
(Oy: 





Equiv. in 50 parts of cold water. 
184 105 Phoronic Ac., C,,H,,0,.—Froths in fusing; gives anhyd. at 190° (m. 
p. 138°). — Lustrous pr. fr. dil. ale.; d.s. h. aq.—CaA, s. h. aq, 
184d. 83 + Phthalic Ac., o-C,H,(CO.H)..—In vablting gives the anhyd. which 


sbl. v. e. and melts at 128°——Rhomb. cryst. s. in 185 pt. aq. at 14°, 
orin 5-5 pt at 99°. §S. in 146 pt. eth. at 15°; e. s. ale.; 1. CHCl. 
—Applyv Test 318!—[The m. p. given (Lossen, A., 144,76), accord- 
ing to Ador (A. 164, 230), holds only for acid that has been pre- 
pared by the usual method of precipitation from a soluble salt. 
A specially purified acid, made from water and the anhyd., is said 
to melt, when in the powdered condition, at 203°.] 


Anisic <Ac., p-MeO.C,H,.CO,H.—B. p. 275°-80°.—Monoclin. cryst. 
Cae Gaerne Peder h. aq.; e. Ss. ale-—BaA, rhombic tbl. d. s. aq.—In 
sealed tube w. conc. HCl at 130° Or fusion Ww. IXOH, gives p-oxy- 
benzoic ac.—Ignition w. BaO gives anisol. 


p-Acetoxybenzoic Ac., C,H,0,.C,M,.CO,H.—Silvery lft. fr. CHC],. 
I, 2, 3-Hemimellitic Ac., C,H,.(CO,H),.—Rather d. s. c. aq.—Ba,A,+ 
5H,O, e. s. aq. (dif. fr. phthalic ac. ) .—Above 185° gives sublimate 


of phthalic anhyd. and benzoic ac.; which hence gives fluorescein 
in Test 402-1 like phthalic ac. 


1-Naphtholcarbonic(2) Ac., HO.C,,H,.CO,H.—Stellate ndl., e. s. eth. 
or bz.; v. d.s. h. aq.—Sol. of KA gives blue color w. FeCl. BaA, 
d.s.aq. Long boiling w. aq. gives CO, and a-naphthol (Test 412). 


Choleic Ac., C,,H,,0,— (In ox-gall.)—-Ndl. fr. h. ale-—Cryst. fr c. alc. 
w. 13H,O, then having m. p. 135°-40°.—S. in 22,000 pt. c. aq.; 
v. d. s. eth.—At 170°-80° gives an anhyd. Boiled w. HCl becomes 
resinous. 


Chrysenic Ac., C,,H,.(Ph)(CO,H)(2, 1).—Lft. fr. bz.; e. s. aic. or eth.— 
BaA,, e. 8. aq. 


Podocarpic Ac., C,,H..0,.—V. d.s. bz.; e. s. eth—Weak ac.—Ca salt 
ignited gives p-cresol—(In a resin fr. Podocarpus Cupressina.) 


G-Methylcumarilic Ac., C,,H,O,.—Ndl. fr. dil. ale-—Sbl.—Rapid heat- 
ing gives CO, and 6-methyleumaron. —BaA,+3H,0, cryst. fr. h. aq. 


Tetrinic Ac., C,H,O,.—B. p. 292° d.—Cryst. s. in 66 pt. aq. at 13-5°; 
e.s.cth. or h. aq.—BaA,+14$H,0, e. s. c. aq.—Reacts w. phenyl- 
hydrazine.—Heated w. KOH at 150° gives much formic (Test 315) 
and propionic ac. (Test 311).—The residue left upon evaporating 
w. dil. NaNO, sol. becomes blue when moistened w. a little conc. 
HNO,. 

m-Cumaric Ac., HO.C,H,.CH: CH.CO,H.—Pr. e. s. h. aq. or eth. 

i-Isocamphoric Ac., C,,H,,0,.—100 pt. aq. at 20° dissolve 0-203 pt. 

o-Cumarilic Ac., C,H,O,.—B. p. 310°-15°.—S. h. aq.; v. s. ale KOH 
fusion gives salicylic acid (Test 319).—RBa salt d. s. aq. 

s-Diethylsuccinic Ac. (fumaroid), CO,H.(CHEt),.CO,H.—Sbl.—V. d.s. 
Coad.) 6.9. eth: —Znk +2H,0, more s. ¢. than h. 

cis-Hexahydrophthalic Ac. (malenoid), C,H,,.(CO,H),.—4-sided pr. fr. 
aq. d. s. aq.—Ba salt less s. in h. than ce. ns 

Ethylfumaric Ac., CO,H.CEt: HC.CO,H.—D. aq.; e. s, eth. 

p- Benzoylbenzoic Ac., Phr.CO. Ci He CO, H; — Sbl. in lft.—D. s. h. aq; 

. eth.— BaA, + 2H,O, d. s. ¢. aq. 
195 166 Pee ina betrolc Ac., EtO.C.H,.CO,H.—Ndl. alm. i. h. aq.—CaA,, ndl 


184-2c. 152 


185 180 
185d. 70 


185-6 188 





185-90 196 


186-5 248 


187-8 274. 


188-9 176 


189 114 


191 164 


192 162 


194 226 


ae a Se 
ee 


fr. h. aq. 
3-Hexenedioic Ac., CO,H.CH,.CH: CH.CH,.CO,H.—Pr. d. s. c. aq. or 
eth. 
s-Dimethylsuccinic Ac. (fumaroid), CH(Me)(CO, H). ance ee 
Ndl. d. s. ¢. aq.; e. s. eth.—Dist. gives anhyd., m. p. 87° 





Se aaa ea nate ee aR SE EE Tig a a Ee UE DLT aL UR i an, ne oe ee 


68 GENUS IIT DIV. A; SECU Ia 


(ORDER I, SUBORDER I.) 








Melting-point Neut. |SOLID ACIDS.—Colorless and gencrally not soluble (cf. note, p. 38) 
(C.°). Equiv. in 50 parts of cold water. 
195 409 Cholic Ac., (CH,OH),.C,.H;,.CH(OH).CO,H.—Cryst. w. 1 aq.—lI. ec. aq.; 


v. d.s. h. aq.; d. s. eth.—Warming w. alittle sugar sol. and conc. 
H,SC, gives a violet-red color! BaA,+7H,O, s. ec. aq.—Aq. sol. 
dec. by CO,.—Oxid. by KMnO,.—To 0-02 grm. ac. in0-5 grm. ale., 
add 1 ce. ;45 normal sol. of I in KI, and gradually dilute w. aq.; 
ndl. w. yellow metallic lustre, blue by transmitted light, separate. 
(Dif. fr. other gall acids.) 

d. 195 96 | Benzalmalonic Ac., Ph.CH:C.(CO,H),.—V. s. h. aq.; ‘‘d. s.” ©. aq.; 
s. eth.—Na,A+ BaCl, gives ppt., sm. ndl. on boiling (no ppt. cold). 
Test 303, at 195°-200° gives CO, and cinnamic ac. (Test 313). 

195d. 87 | Tetramethylsuccinic Ac., CO,H.(CMe,),.CO,H.—100 pt. aq. at 13-5? 
dissolve 0-48 pt.; s. eth.—Fusion gives anhyd. w. camphor-like 
odor, m. p. 147°. 

d. 195-200 170 | Pyrogallocarbonic Ac., C,H,(OH),.CO,H(2, 3, 4, 1).—Silky ndl. fr. h. 

aq.; s. 767 pt. c. aq.; v. s. eth.—Colored violet by v. dil. FeCl,.— 
Reduces ammon. AgNO, sol. in the cold.—(Cryst. w. 4+H,O.) 





196-7d. 108 | Cineolic Ac., C,,H,,0;—Cryst. s. in 70 pt. c.aq.; e. s. eth.—Dec. by 
heat to CO, and an ac. C,H,,O,.—(An oxid. product of cineol.) 
197 162 | p-Methylcinnamic Ac., Me.C,H,.CH: CH.CO,H.—Mod. s. h. aq.—Nadl. 
een en a 
199 154 | Protocatechuic Ac.—Cf. Ac. of Sect. 1. 
199 Lithobilic Ac., C,.H;,0,.—Mic. cryst. e.s. ale.; i. aq.; s. eth. Warm 


conc. HCl colors intense red-violet.—Gives Pettenkofer’s reaction, 
—BaAa,+6H,y, i. aq. 

199 166 1, 2-Dimethylphenol(5)carbonic(4) Ac., Me,.C,H,(OH).CO,H.—Ndl. d. 
s.h. aq.; e. s. alc. or eth.—Gives intense blue-violet color w. 
FeCl,! BadA,, d. s. c. aq. 


200 5U4 | Triphenylcarbinol-p-carbonic Ac., Ph,.COH.C,H,.CO,H.—I. aq.; e. s. 
eth.—Ra salt v. d. c. s. aq. 

200 174 | y-Methylindene-@-carbonic Ac., C,,H,,O,—Ndl. fr. ale—Warmed w, 
MnO, and cone. KOH gives a blue solution. 

200 138 | t{m-Oxybenzoic Ac., HO.C,H,.CO,H.—Dist. undec. Tastes faintly 


sweet (dif. from para acid).—S. 108 pt. aq. at 18°.—No color w. 
FeCl,.—_CaA, + 3H,0, s. aq.—0-02 grm. boiled w. 5 ce cone. H,SO, 
gives orange-red (OR) sol. (Dif. fr. o- and p-ac , the o-acid giv- 
ing only pale-vellow, and the p-acid giving orange-yellow (OYTI) 
when treated in this way.) 





200 164 | p-Acetylbenzoic Ac., Me.CO.C,H,.CO,H.—Sbl.— Ndl. rather d s. h. aq.; 
e. s. eth.— BaA, + 4H,0, s. h. aq. 

201 298 | Picenic Ac., C,,H,.C,,H,.CO,H.—Flocks fr. ale.; s. ale. or CHCl;.— 
Heated w. Ca(OH), (i. v.) gives $-binaphthyl. 

201 [—]Camphanic Ac., C,,H,,0,—Rhombohedra fr. eth.—Volat. w. st.— 


Sbl. easily fr. 110°.—W. aq. at 180° gives CO, and a hydrocarbon 
Ug ble Dual aves 





203 302 4-Methyltriphenylmethane-2-carbonic Ac., C.,H,.0,.—Dist. undec.— 
Ignition w. Ba(OH), gives p-methyltriphenylmethane. 
204 212 | m-Tolylbenzoic Ac., Me.C,H,.C,H,.CO,H. 

204-5 Lithofellic Ac., C,,H,,0,—(Cryst. w. 1H,O fr. 33% ale.)—S. h. ale. or 
h. eth. Gives intense red color w. cone. HCl.—(Found in ben- 
zoars. ) 

204-5 92 Methylfurfurancarbonacetic Ac., C,HO.(Me)(CO,H)(CH,.CO,H).—Sbl. 


undec.—Short ndl., v. d. s. c. aq.; e. s. alc.; s. eth—NH, salt 
heated gives pyrrol-red.—CaA, cryst. ppt. 1. h. aq. 





Oe ee 





Melting-point Neut. 
enon Equiv. 
204-6d. 154 
205d. 91 
205-10d. 
206 198 
206 164 
206 97 
206d. (s. h.) 
206d. 222 
206-7c. 152 
207 168 
208 164 
208 100 
210 138 
abt. 210 198 
210-1 188 
210-5 192 
PAWS 86 
215 85 
215 164 








GENUS III, DIV. A, SECT. 2. 


(ORDER I, SUBORDER I.) 





SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 
in 50 parts of cold water. 





2, 4-Dioxybenzoic Ac., (OH),.C,H,.CO,H.—Cryst. w. 3H,0.—S. 381 pt. 


aq. at 17°.—Aq. sol. colored violet by little Ca(OCl), sol.—BaaA, e. 
8. aq.—PbAc, gives no ppt. 

Furalmalonic Ac., C,H,0.CH:C.(CO,H),.—Pr. alm. i. c. aq.; s. ale. or 
eth.—AgA; curdy ppt.—Loses CO, on fusion, giving furfurol 
acrylic ac. . 

Coumalic Ac., C,H,0,.CO,H.—Sm. pr. d. s. c. aq.; s. ale. or eth.—Re- 
duces ammon. AgNO, or Fehling’s sol. on warming.—Beiled w. dil. 
H,SO, gives crotonic ald.—Boiling aq. sols. of salts gives carbonates, 

$-Isoatropic Ac., C,.H,,0,.—Thbl. fr. h. aq.— Cryst. ppt. w. BaCl,.—Con- 
tinued heating at 225° gives a-ac., m. p. 237° 

p-Cumaric Ac., HO.C,H,.CH:CH.CO,H.—V. d.s.c., e. s. h. aq.; v.s. 
eth. or alc.—Ale. sol. becomes golden brown w. FeCl,;—Fusion w. 
KOH gives p-oxybenzoic ac. 

2, 6-Dimethylterephthalic Ac., Me,.C,H,.(CO,H),.—Ndl. fr. alc.; e. s. 
eth.—Sbl undec.—BaA+3H,0O, pearly lft. 

t+ Mucic Ac., CO.H.(CHOH),.CO,H.—Sandy cryst. powder s. in 300 pts. 
aq. at 14°; i. ale —+ Mix 0-01 grm. acid w. 5 drops conc. ammonia 
in 5-in. test-tube. Evaporate to dryness. Hold soft pine splinter 
that has been soaked in conc. HCl for several min. in upper part of 
tube, and ignite residue strongly. Pyrrol vapors evolved develop 
bright-red color in splinter! (‘‘ Pyrrol reaction,’—a simple test, 
but also given by some other substances )—(M. p. higher w. rapid 
heating.) 

a-Anthracenecarbonic Ac., C,,H,,O,.—Silky pale-yellow ndl, d. s. h. 
aq.—Br subst. easily. Oxid. by CrO, in Ac sol. gives anthraquinone. 
—Dist. w. soda lime gives anthracene (Test 912). 

2-Oxy-p-toluic Ac., HO.C,H,Me.CO.H.—E. s h. aq; s. eth.; i. CHC]. 
—Sb!.—Gives no color w. FeCl,.—Ignited w. CaO gives o-cresol. 

+ Vanillic Ac., C,H,.(Me0O)(OH)CO,H.(3, 4, 1).—Ndl. fr. h. aq.; s. 
850 pt aq. at 14°; e s. eth —Odorless if pure.—Gives no color w. 
FeCl,.— Salts w. exception of those of Pb and Ag generally soluble. 
—AgA blackens in h. aq.—Dist of Ca salt w. slacked lime gives 
pure guiacol (cf. p. 91) 

o-Coumaric Ac., HO.C,H,.CH: CH.CO,H.—D. s.c. aq.; d.s.eth; e.s. 
ale.—Sbl.—Dec. on dist. into CO, and phenol. (Test 414.)— 
Fusion w. KOH gives salicylic and acetic acids —Dil. ammonia 
gives a yellow sol.. pale green by reflected light——FeCl, gives a 
yellow-red ppt —BaA,+H,0, e s. aq. 

i. Camphoric Ac., C,,H,,0, —Difficult to eryst.—100 pt c. aq. dissolve 
0-239 pt.; v s. eth.—Ba salt ndl. s. in 10 pt. aq. 

+ p-Oxybenzoic Ac., HO.C,H,.CO,H.—Pr w 1H,O fr h aq. S8.in 126 
pt. aq at 15° —Gives amorph, yellow ppt w. FeCl, —Dist. dec 
to phenol (Test 414) and CO, —Taste not sweet like that of meta ac. 

a-Naphthylacrylic Ac., C,,H;.CH:CH.CO,H.—I h. aq. 

a-Oxy-@-Naphthoic Ac., HO.C,,H,.CO,H.—Ndl s h. aq.—Gives dirty- 
red ppt. w. FeCl,, becoming black on boiling, 

Pentamethylbenzoic Ac., Me,;.C,.CO,H.—Cryst. fr h. 
Methylester m. p 67 5°. 

T trans-Hexahydrophthalic Ac. (fumaroid), C,H,,.(CO,H),.—Lfts. s. 
in 434 pt. c. aq.—C. alk. permanganate does not attack —Ca salt 
ie. cag, 

A?-Tetrahydrophthalic Ac., C,H,,0,.—S. in 114 pt. aq. (10°). Decol- 
orizes alkaline permanganate sol. at once in the cold, forming 
oxalic ac and succinic ac. 

I, 2, 3-Irimethylbenzoic(5) Ac., Me,.C,H,.CO,H.—Cryst. v. d. s. h 
aq.; s. eth.—Ca salt d. s. c. aq.—Ignited w. CaO gives 1, 2, 3- 
Me;.C,Hs. 


a 





aq —Sbl.— 














70 GENUS Ilr, DIV. A, SECT. 2 
(ORDER I, SUBORDER I.) 
Melting-point Neut. [SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 

(C2). Equiv. in 50 parts of cold water. 

215 84 | 42) *-Dihydrophthalic Ac., C,H,.(CO,H),..—Pr. v. d. s. c. aq.; e. s. 
h.—BaA, s. c. aq., less s. h. aq. 

215-6d. 247 Santononic Ac., C,,H;,0,.—Pearly lft. fr. alc.; i. aq.; e s. ale.; d,s. 
eth.—Ag,A, ppt. 

216 188 | Oxynaphthoic Ac., C,,H,.(OH).CO,H(2, 3).—E. s. alc., eth—Rhemb., 
lft. fr. h. aq.; e. s. eth.—Sol. becomes blue w. FeCl, ! 

216-7 206 | Piperic Ac.—Pale-yellowi 

217 302 | 3-Methyltriphenylmethane(6)carbonic Ac., Ph,.CH.C,H,(Me).CO,H. — 
Tbl. fr. eth. or ale., i. aq.; e. s. ale. or eth.—Dist. undec.—Ignited 
w. Ba(OH), gives m-methyltriphenylmethane.—BaA,+H,0O, i. 
ppt. 

218-9 198 | p-Phenylbenzoic Ac., Ph.C,H,.CO,H.—Sbl. in ndl.—y. d. s. h. aq.; 

e. s. alc. or eth. BBE Soe lit. vs ‘d. s. h. aq. 

219d. 100 | Diphenylmethanetricarbonic Ac., (CO,H.C,H,),.CH.CO,H.—S. h. aq.— 
M. p. of trimethylester 145°. 

220-1 91 Camphoric Anhyd., C1 Hl. -—B. p. a. 270° (undec.). Long rhomb. 
pr. fr. ale.—V. "d's. aq.—Boiling aq. slowly gives camphoric ac., 
v. d. s. aq.m. p. 187°.—Opt. inact. 

221 210 | Diphenyleneacetic Ac., (C,H,),CH.CO,.H.—AIm. i. aq.; e. s, alc. or eth_— 
Ignition w. CaO gives fluorene. 

223 166 | 1, 3-Dimethylphenol(2)benzoic(5) Ac., Me,.C,H,OH.CO,H. — Sbl. — 
Hair-like ndl. fr. h. aq.; e. s. eth.—BaA, mod. s. ¢. aq. 

227 - 5-28 166 | Piperonylic Ac., CH,.0,.C,H,.CO,H.—Sbl. in pr.; ndl. fr. ale.; d.s. h. 
aq., c. alc. or eth.—CaA,+3H,0, s. in 161 pt. aq. at 15°—Aga 
cryst. ppt. s. h. aq. 

228 194 | Isoferulic Ac., C,H;.(C,H,.CO,H).(QH)(MeO). Cr 3, 4).—Ndl. d. s. c. 
aq.; e. 8. alc. or eth.—_CaA, +2H,0, d. s. nd 

228 148 y-Truxillic Ac., C,,H,,0,—V. d. 8. aq.; e.s. oe gives cinnamic 
ac. (cf. Test 313). Alkaline permanganate gives benzoic ac. (Test 
312).—Ag,A ppt. — 

229 121 Biphenyl-1,10-dicarbonic Ac., (Diphenic Ac.). CO,H. C, all ,.-Gort i COnes 
—Sbl. in ndl. §S. h. aq.; e. s. eth. — Bai +4H,0, €. 8. tore" 
Heated w. Zn dust gives diphenyl. 

abt. 230 160 | Indenecarbonic Ac., C,,H,O,.—Sbl.—V. s. eth. 

230-1 90: +) 355 5- Dinmethylfurandte ayaa 4) (Carbopyrotritaric) Ac., 
Me,.C,0.(CO,H),.—Sm. ndl. fr. h. aq., alm. 1. c. aq.; e. s. alc.; 
s. eth.; v. d. s. CS,.—Fusion w. KOH gives succinic ac. (Test 320) 
and acetic ac.—CaaA+BaA, cryst. ppts. fr. h. aq.; Ag,A, ppt. 

222-40d. { Gallic Ac., (HO),.C,H,.CO,H(3, 4, 5, 1).—Cryst. w. 1H,O (lost at 
120°) in silky ndl. S. 180 pt. aq. at 12-5°.—Aq. sol. absorbs O from 
air and turns brown during titration; gives no ppt. w. sol. of 
gelatine (dif. fr. tannic ac.). 

234-7 188 a, a-Oxynaphthoic Ac., HO.C,,H,.CO,H.—Sbl.—S. h. aq.; e. s. ale.— 
Fusion w. CaO vives a-naphthol (Test 412).—Aq. sol. gives dirty- 
violet ppt. w. FeCl,. 

237 148 | a-Isoatropic Ac., C,,.H,,0,—V.d.s h. aq.; alm. i. eth—CaAa,+2H,0, 
alm. i. ppt.—Warm conc. H,SO, gives CO. CrO; gives anthraqui- 
none (Test 1011). 

237-8 90 | Homoterephthalic Ac., p-CO,H.C,H,.CH,.CO,H.—S. h. aq.; alm. i. eth, 
—Ag,A, cryst. ppt. 

238 154 | 2, 5-Diphenylfurandicarbonic(3, 4) Ac., C,O(Ph),.(CO,H),.—D. s. aq.; 
e. s. ale. or eth.—Sol. in cone. H,SO, becomes blue on warming !— 
Ignition w. soda-lime gives acetophenone (Test ae 

243 212 | p-Phenyltolylcarbonic Ac., Me.C,H,.C,H,.CO,H.—D. s. h. aq. 

243 91 ! 2-Oxyisophthalic(1, 3) ae -, HO.C,H,. (CO oll )os ~ Gevah w. 1H,0. — 


.h. aq.; v. d.s. c. aq.; e. s. eth.—Aq. sol. cherry red w. FeCl, 1 
Solutions fluoresce blue-violet ; color destroyed by alkali.—Dist, 
gives CO, and salicylic ac. (Lest 319). 








GENUS 111, DIV, a. SECT 8, ‘1 


(ORDER I, SUBORDER 1.) 





Melting-point 
ear 





245 
247 
250 


250d. 


251 


(r. h.) 252d. 
250-60 
256d. 


255-60 


d. 260 


d.a. 260 


261d. 

262d. 

264d. 
266 
267 
270 


abt. 270 
(m. p. of anhyd.) 


Neut. 
Equiv. 


210 


150 
168 


140 


222 


135 


292 


162 


180 


211 

92 
294 
222 
237 
230 


108 


148 
99 
97 


196 


SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 


in 50 parts of cold water. 


Fiuorenic Ac., C,,H,,0O,.—Sbl. undec.—Alm. i. h. aq.; e. s. h. ale.— 
BadA,+3H,0, lft. d. s. ec. aq.—Ignition w. CaO gives fluorene. 

Isocholanic Ac., C,,H,,0,,—Pearly scales alm. i. aq. or eth.; e. s. ale.-— 
Ba,A, d. s. h. aq., not pptd. by CQ). 

Isovanillic Ac., C,H;.(Me0O)(OH)CO,H(4, 3, 1).—Sbl. undec.; alm. i, 
c. aq.; d.s. h. aq.—Gives yellow color w. FeCl). 

Comanic Ac., C;H,0,.CO,.H.—D. s. aq.—No color w. FeCl,.—BaA,, 
e. s. aq.—Boiled w. baryta water gives acetone (Test 711), oxalic 
(Test 317) and formic (‘Lest 315) acids. 

$-Phenanthrenecarbonic Ac., C,,H,.CO,H.—Sbl.—Alm. i. aq.; s. eth, 
—Baa,+ 6H,0, v. d. s. c. aq.—Ignition w. soda-lime gives phenan- 
threne (cf. Test 916).—Oxid. w. CrO, gives phenanthrenequinone 
(cf. Test 1013). 

f-Bibenzyldicarbonic Ac., C,,H,,.(CO,H),.—Ndl. fr. alc.; i. aq.; s. in 
89 pt. abs. ale-—CrO, oxid. to benzoic ac. (Tests 905-2 and 3).— 
Ba salt e. s. aq. 

Lactic Anhyd., C,H,O,,CO,H.—Yellowish amorph. mass alm. i. aq.; 
e. s. alc. or eth.—Alkalies immediately give lactic-acid salts — 
Heated, dec. to CO, CO,, lactide and citraconic ac. ; 

8-o-Oxynaphthoylbenzoic Ac., HO.C,,H,.CO.C,H,.CO,H.—V. d. s. h. 
aq.; e. s. alc. or eth—Fusion w. KOH gives /-naphthol and 
phthalic ac. (Tests 413 and 318). 

p-Isopropenylbenzoic Ac., CH,:CMe.C,H,.CO,H.—Nadl. d. s. c. ale.— 
BaA,+H,0, amorph. ppt.—Br, adds very slowly. 

Umbellic Ac., C,H;.(OH).(CH:CH.CO,H)(2, 4, 1).—S. h. aq.; i. eth— 
Browns at 240°.—Reduces ammon., AgNO, on warming.—BaA, 
s. aq.—AgA becomes resinous on boiling.—FeCl, gives dirty-brown 
coloration. 

Comenic Ac., HO.C,;H,0,.CO,H.—S. 16 pt. h. aq.; i. abs. ale.—Pale-yel- 
lowish crusts.—Dec. by heat gives CO, and pyromeconic ac.—Brsub- 
stitutes readily.—Red color w. FeCl,.—Ag,A yellow ppt. fr. NH, salt. 

Tetraphenylsuccinic Ac., CO,H.(CPh,),.CO,H.—E. s. eth. 

2, 6-Pyrondicarbonic [Chelidonic] Ac., C,H,O,.—Silky ndl. w. 1H,0O fr. 
h. aq.; d.s. c. alc-—Many salts yellowish.—Boiling w. milk of lime 
gives acetone (Test 711) and oxalic ac. (Test 317). 

Triphenylacetic Ac., Ph,.C.CO,H.—Softens at 230°.—Ignition w. CaO 
gives triphenylmethane. 

a-Phenanthrenecarbonic Ac., C,,H,.CO,H.—Lft. fr. h. Ac_—Reactions 
like B-ac. (m. p. 251°). 

Pyrenecarbonic Ac., C,,H,.CO,H.—Sbl.—Yellowish warty mass, s. h. 
alc. or eth.—Heated w. CaO gives CO, and pyrene. 

Biphenyldiol(3, 8)-carbonic(1) Ac., HO.C,H,.C,H,(OH).CO,H.—Gives 
green color w. Ca(OCl), sol— Gives chocolate ppt. w. FeCl,. 

Naphthalic Ac., C,,H,.(CO,H),(1, 8).—The anhyd. is formed at 150° 
without melting.—Silky ndl. fr. ale.; alm. i. aq.; d.s. eth.—Igni- 
tion w. CaO gives naphthalene (Test 915).—The anhyd. dissolves 
in conc. H,SO, w. blue fluorescence, and boiled w. conc. NH; gives 
the imide of m. p. 300°. 

2, 4-Diphenylcyclobutanedicarbonic(1, 3), (a-Truxillic) Ac., C,,H,,0,. 
—wNdl. s. eth. or h. ale.—Dist. gives cinnamic ac. (Test 313). 

a-Resodicarbonic Ac., (HO),.C,H,.(CO,H),.—Cryst. v. d. s. h. aq.; s. 
eth.; gives blood-red color w. FeCl, sol. 

Hydrocinnamic-p-carbonic Ac., CO,H.C,H,.(CH,),.CO,H.—Sbl.—S. h. 
aq. or alc.—Gives nitro-deriv., m. p. 191°-2°, 

Cantharic Ac., C,H,,0O.CO.CO,H.—Cryst., s. 120 pt.c., or 12 pt. h. aq.; 

v.s. ale.;. alm. 1. eth.—AgA ppt.—The imide, by heating w. 56 pt. 

alc. NH, at 150°, forms tbl. fr. alc., m. p. 187°.—Ignited w. CaQ 

gives CO, and cantharene (C,H,,). 


72 


GENUS. IM], “DIV, A, SHCT.2. 


(ORDER I, SUBORDER I.) 


a 


Melting-point 
COS). 
278 


280-3 


283 
285d. 
287-8 


288c. 


290 


abt. 290 u. ec. 
sblg. 


290d. 


305 


d. abt. 320 


320-30 


a. 300 


a. 300 
much a. 300 


Sb. w. m. 
345-50 


Sb. w. m. 





Neut. 


Equiv. 


166 


90 


252 


90 


91 


108 
108 


83 


70 


68 


Triphenylmethanedicarbonic(2, 4) 





SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 
in 50 parts of cold water. 

. Ac., Ph,.CH.C,H;.(CO,H).. — Ig- 
nited w. Ba(OH), gives triphenylmethane.—Cad + 2H,0, ppt. 
Methyltcrephthalic Ac., C,H;.(Me)(CO,H).,(1, 2, 5).—Sbl. below 280°. 

—BaaA v.e. 8, aq. 
G-Anthraquinonecarbonic Ac.—Cf. Suborder 2. 


Cholanic Ac., C,,H,,O, (?).—Pr. fr. alc., s. in 4000 pt. h. aq.—Sol. in 
conc. H,SO, fluorescent. Opt. act.—AgA, curdy ppt., Ba salt 
Ss. aq. 

s-Uvitic Ac., C,H;.(Me)(CO,H),(1, 3, 5).—Sbl.—Ndl. fr. h. aq.,e. 8, . 
cth.—LaA+H,0, e. s. aq.—Ignition w. CaO gives toluene (Test 
918)! 

5-Oxyisophthalic(1, 3) Ac., HO.C,H;.(CO,H),.—(Cryst. w. 2H,O.)— 
Sbl.—E. s. eth. or h. aq.—Gives yellowish-brown color w. FeCl,.— 
Ignition w. CaO gives phenol (Test 414). 


Diphenylmethanedicarbonic Ac., CH».(CsH,.CO2H)2(z : 4)2 
+ Fumaric Ac., CO.H.CH : CH.CO.H.—Cryst. s. 148.7 pt. aq. @ 16.5°. 
Reacts unsat. in Test 302; but adds Br. w. difficulty —Above m. p. 


gives maleic anhyd. w. sl. decen—Mena : cryst. fr. dil. ale.; m.p. 
102°; (fr. acid+MeOH-+dry HCl) —Baa.13H20 : s. 100 pt. c. aq. 


m-Oxyuvitic Ac., HO.C,H,(Me)(CO,H),.—E. s. eth. or h. aq.—Gives 
reddish-violet color w. FeCl,.—BaA, e. s. aq. 

4-Oxyisophthalic(1, 3) Ac., HO.C,H,.(CO,H),.—D. s. h. aq.; e. s. eth. 
—Aq sol. becomes cherry-red w. FeCl,.—Destructive dist. gives 
phenol and salicylic ac. (Test 319). 


Muconic Ac., CO,H.CH:CH.CH:CH.CO,H.—S. 5000 pt. c. aq.— 
Me,A, m. p. 154°. 

1-Methylisophthalic(2, 4) Ac., Me.C,H,.(CO,H),.—Sbl. in thick glassy 
eryst —D. s. h. aq.; s. h. alce——Gives no anhyd.— Baa +2H,0, 
e. s. aq. or alc. 


{ Isophthalic Ac., m-C,H,(CO,H),.—Sbl. undec. without forming an 
anhyd.—Hair-like ndl. fr. h. aq.—S. in 7800 pt. aq. at 25°, or 460 
pt. h. aq.; s. ale-—BaA+6H,0, triclinic cryst., v. s. ag. and efflo- 
rescent !—Ag,A amorph. ppt., alm. i.h.aq.; swells like a zeolite on 
heating.—Apply Test 318-2! 

$-Naphthalenedicarbonic Ac., C,,H,.(CO,H),.—Alm. i. h. bz. or Ac.— 
Ca salt v.d.s. cryst. ppt. 

a-Naphthalenedicarbonic Ac., C,,H,.(CO,H),.—Closely resembles $-acid 
(above).—Salts somewhat more soluble. 

t Terephthalic Ac., p-C,H,.(CO,H),.—Powder.—S. in 67,000 pt. c. aq.; 
alm. i. alc. or h. aq. !—Alm. i. eth. or CHCl,—BaA+4H,0, tbl. 
v. d. s. (1:355-4 at 5°) !Ag,A ppt.; CaA+3H,0, alm. i. c. aqg.— 
Apply Test 318-3! 

s-Trimesic Ac., C,H;.(CO,H);.—Solubility in aq. at 22-5°, 2.69%; at 
16°, 0-38%; v.s. ale.—Sbl. at 300°.—BaA,+ H,O (at 150°); alm. 
i.c. aq.; v. d. s. h. aq. (dif. fr. iso- and tere-phthalic acids).— 
Me,A (fr. Ag,A and CH,I), m. p. 148°. 

Furfuranedicarbonic (Dehydromucic) Ac., C,H,0,;.—Ndl. fr. h. aq. (dif, 
fr. terephthalic ac.). V.d.s. alc.; d.s. eth.—Aq. sol. warmed w. 
FeCl, in absence of mineral acids gives a transparent jelly.—BaA + 
24H,0O, s. h. aq.!-—Dry dist. gives pyromucic ac. 





ee LA, 


COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER Jj 
GENUS III, ACIDS. 


DIVISION B, SECTION 1,—LIQUID ACIDS SOLUBLE IN COLD 
WATER. 


Boiling-point Neut. [LIQUID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in 
(C2), Equiv. 50 parts of cold water. 


32-3 60 {| Methyl Formate, H.CO,Me.—G.‘0-9984°/,.—S. aq.—Saponified very 
easily and may be slowly titrated like a monobasic ac.—Test for 
methyl ale. by Test 819-1, and for formic ac. by boiling the neutral 
solution resulting from the titration for neut. eq. with AgNO. sol. 
Ag will be ppt’d. 

100-8 46 | {+ Formic Ac., H.CO,H.—G, 1-2448°/,—M. p. +8-6°.—Misce. w. aq.— 
Neutral salts all s. in aq.—Odor very charp.—Gives Test 304.— 
Apply Test 315! 

118-1c. 60 t Acetic Ac., Me.CO,H.—G. 1-051?°/,).—Solidifies at 16-7°. Misc. w. 
aq.; neutral salts all s. in aq.—Sharp odor.—Does not give Test 
304. Apply Test 311! 

nye 51 | + Acetic Anhyd., (Me.CO),.0.—G. 1-0969 at 0°.—Sharp and irritating 
odor. 8. c. aq. and v. slowly decomposed by it.—For behavior on 
titration cf. p. 37! Identify by Tests 307 and 311! 

139-6 Acetylacetone, CH,.CO.CH,.CO.CH,.—Cf. IV, B. (A weak acid.) 

140 36 | Acrylic Ac., CH,:CH.CO,H.—G. 1-0621'°/,—M. p. +8°.—Sharp odor 
like Ac.—Gives Test 304.—PbA, lustrous ndl. s. in ale—KOH 
fusion gives formic and acetic ac. (Tests 315 and 311). 


140-7e. 74 | + Propionic Ac., C,H,;.CO,H.—G.0-996!/,,.—M. p. —22°.—Odor like Ac. 
—Salts all soluble-——Does not give Test 304.—Apply Test 311! 
144d. 70 | Propiolic Ac., CH:C.CO,H.—M. p. +6°.—S. aq., ale., or eth.—Strong 


acetic-acid odor.—Dec. by sunlight.—Gives Test 304. Addition 
product w. Br, has m. p. 85°.—Explosive brown ppt. w. ammon. 
CuCl sol. (Test 906) !—Reduces AgNO, sol.—Salts v. s. aq., but 
the solutions are dec. by boiling. 


144-8 Methyl Lactate, C,H,O,.—G. 1-118 at 0°.—Sapon. gives lactic acid (cf. 
p. 39), and methyl! alc. (Test 819-1). 
154-5 Ethyl Lactate, C;H,,0,.—G. 1-055 at 0°.—Sapon. gives lactic acid (cf. 
p- 39) and ethyl alc. (Test 814). 
155 88 { Isobutyric Ac., Me,.CH.CO,H.—G. 0-9487'*8/,—S. in 5 pt. aq. at 


20°.—Unpleasant odor like rancid butter.—Aq. sol. of the v. s. 
Ca salt does not become turbid on boiling (dif. fr. normal Ca salt). 
—Salts are ail more soluble than those of the normal acid.—May 
be oxid. by alkaline permanganate to acetonic ac. (a reaction’ 
used by V. Meyer to detect it in presence of much normal acid).— 
Identify by Test 311! 

162-3 86 | Methacrylic Ac., CH,:CMe.CO,H.—G. 1-0153?°/,—M. p. +14°.— 
S. aq.—Gives Test 304.—Heated for some time in tube at 130° 
polymerizes to a porcelain-like mass which dec. above 300° —CaA,, 
e. s. aq.—Na amalgam gives odor of isobutyric ac. 

162-5 88 + n-Butyric Ac., C,H;,.CO,H.—G. 0-95991*!/, —Miscible w. aq. (dif. fr. 
isobutyric ac.), ale., or eth—M. p. —7-9°. Unpleasant and per- 
sistent odor of rancid butter.—Prepare a clear sat. sol. of the e. s. 
Ca salt by neutralizing a solution of the acid w. an x's of CaCO,, 
concentrating, allowing to stand for some time in the cold, and 
filtering. The cold saturated sol. gives a white ppt. when warmed 

(dif. fr. isobutyric ac.).—Identify by Test 311! 





73 


74 GENUS UL DIV, Basten. 


(ORDER 1, SUBORDER I.) 








Boiling-point Neut. |LIQUID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in 
COR F 





Equiv. 50 parts of cold water. 
165s. d. 88 | } Pyruvic Ac., Me.CO.CO,H.—G. 1-288 at 18°.—Misc. w. aq., alc., or 


eth.—Sharp odor like Ac .—Readily attacked by Br or KMno,,. — 
Mixed w. equivalent quantity of phenylhydrazine dissolved in 
5 pt. ether gives a hydrazone, cryst. fr. alc., m. p. 192° (r. h.).— 
Mirror w. ammon. silver sol.—Salts fr. boiling solutions are 
gummy.—For color reaction w. sodium nitroprusside and ammonia, 
ef. Compt. rend. 125, 534. 


168 86 Buten(1)oic(4) oe C,H,.CO.H.—CaA,+H,0, lft. fr. h. aq.; cryst. 
fr. c. aq. w. 2H,O.—Gives Test 304. 
169-9-3 86 | tIsocrotonic Ac., Me.CH:HC.CO,H.—G. 1-0312'*/,—S. in 2-5 pt. 


aq.—Odor sharp! Gives Test 304.—CaA,, s. aq.; AgA, curdy. 
ppt.—t Heat 0°5 cc. of the acid w. 5 mgr. iodine for 1 hour in a 
dry test-tube whose lower end is immersed in an oil-bath at 150°. 
Dissolve product in 1 cc. hot ligroin, Cool w. ice-water. Drain 
crystals which separate on porous tile. Wash w.a few drops cold 
ligroin, and dry. The crystals are crotonic acid, and melt at 72°. 
(uncor.) ! 
176c. 102 | Isovalerianic Ac., Me,.CH.CH,.CO,H.—G. 0-9467 at 0°.—M. p. —51°.— 

S. 23-6 pt. aq. at 20°; misc. w. alc. or eth.—Odor offensive like 
decayed cheese !—Alkali salts give no ppt. w. CaCl; gelat. p 
w. ZnSO, in the cold, or scales if hot; v. d. s. eryst. ppt. w. AgNO. 

177 (th. 1.) 102 | Methylethylacetic Ac., Et.CHMe.CO,H. sey 0 -938?°/..—Feeble odor of 
isovalerianic ac.— Not solid at —80° .—CaA,, s. aq.—ZnA, more 


s. c. than h. 
182 86 | Trimethylenecarbonic Ac., C,H,.CO,H.—G. 1-0879%°/,—M. p. 17°.— 
‘*Somewhat”’ s. in aq. 
186-6-4c. 102 | n-Valerianic Ac., Me.(CH,),.CO,H.—G. 0-9577 at 0°.—M. p. —58-5°. 


—Odor and solubilities of ac. and its salts nearly the same as for 
isovalerianic ac. (cf. above). 
186-1c. 146 | + Diethyl Oxalate, C,0,.Et,—G. 1-0815 at 18-2°—Titrates w. deci- 
normal NaOH like monobasic ac.—Shaken w. conc. ammonia 
gives an immediate heavy cryst. ppt. of insol. oxamide !—Saponify 
(Test V), and test for ethyl alcohol (Test 814), and oxalic ac. 
(Test 317). 
190 116 | Methylisopropylacetic Ac., Me.CHPr.CO,H.—G. 0-928 at 15°.—CaA, 
less s. in h. than in ec. aq. ; 
190 (th. 1.) 116 Diethylacetic Ac., Et,.CH.CO,H.—G. 0-9355 at 0°.—CaA,, e.s.; ZnA 
more s. c. than h, 
191 (th. i.) 103 | 1-Methyltrimethylenecarbonic(2) Ac., C,H,.CO,H.—G. 1-015'8/,.—S. 
in 12 pt. aq. at 15°.—BaA,+2H,0, ndl. v. S. Cc. aq. 





2 


193 116 | Methylpropylacetic Ac., Me.CHPr.CO,H.—G. 0-9414 at 0°—CaA,, 
s.aq.; FeA, flesh-red ppt. s. in x’s FeCl. 
194 100 Pentene(2)-oic(1) Ac., Me.CH,.CH:CH.CO,H.—G. 0-992 at 15°.—M. 


p. 9-5 °-10-5°.—S. in 16 pt.c.aq.—Gives Test 304.—CaA,+H,0, 
e. Ss. aq., alc., or eth.; AgA voluminous ppt. 


195-8d. 118 a-Ethoxypropionic Ac., Me.CH(OEt).CO,H.—HE. s. aq., alc., or eth.— 
CaA,+2H,0O, e. s. aq.; AgA fine silky ndl. mod. s. c. aq.; views 
hag; 

200-1 100 | Penten(2)oic(1) Ac.,C,H,.CO,H.—G. 1-0074 at 0°.—Lft., m. p. 10°.— 
Sharp odor.—Gives Test 304.—S. in 16 pt. aq.—Ba salt v. s. aq. 

203 90 | Methoxyacetic Ac., MeO.CH,.CO,H.—G. 1-18.—Misc. w. aq.—PbA,, 

s. aq. and alc. 

206-7 104 Ethoxyacetic Ac., EtO.CH,.CO,H.—S. aq.—CaA,+2H,O v. s. aq. or 
alc. 

213-20 132 | $-Ethoxybutyric Ac., Me.CH(OEt).CH,.CO,H. 


239 (sl. d.) 116 | + Levulinic Ac., Me.CO.(CH,),.CO,.H.—M. p. 33°.—Gives iodoform in 
the cold in Test 801.—Cf. Div. A, Sect. 1. 


275 (sl. d.) 130 y-Acetylbutyric Ac., Me.CO.(CH,);.CO,H.—Deliquesces to hydrate 
Ww. m. p. 35°-36°. 








COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I} 


GENUS III, ACIDS. 


DIVISION B, SECTION 2,—LIQUID ACIDS NOT SOLUBLE IN 





Boiling-point 
(Ge). 


168-6 


181 


182-5 


187 
188 (th. i.) 


189-91 
191-3 


195 


197 (th. i.) 
200-5 


202—4 
205: 7c. 


206-5 (th. i.) 
207-8 
207 + 7c. 
209 
209 - 2c. 


210 


COLD WATER. 





Neut. |LIQUID ACIDS.—Colorless and generally not soluble @f. note, p. 38) 


Equiv. 


65 


132 


79 


116 


100 


116 
-79 


100 


116 


114 
116 


114 
130 
116 
130 
130 


130 


in 50 parts of cold water. 


{ Propionic Anhyd., (Et.CO),0.—G. 1-0169 at 0°.—Sharp and irritat- 


ing odor.—Il or behavior on titration cf. p.37.—D.s. c. aq. and v. 
slowly dec. by it.—Identify by conversion into propion-p-toluide 
(cf. p. 81) either by heating w. p-toluidine directly or by methods 
of Tests 307 and 311! 

a-Ethoxyisobutyric Ac., Me,.C(OEt).CO,H.—G. 1-0211 at 0°.—D. s. c., 
e. 8. h. aq.—BaA,+H,0, s. alc. or h. aq.—ZnA,, lft., e. s. alc. or eth. 

Isobutyric Anhyd., (Me,.CH,.CO),.0.—G. 0-9574 at 16-5°.—For be- 
havior on titration cf. p. 37—Convert into isobutyr-p-toluide 
(cf. p. 81) either by heating directly w. p-toluidine or by methods 
of Tests 307 and 311! 

Dimethylethylacetic Ac., Me,.CEt.CO,H.—V. d. s. aq.—BaA,+5H,O, 
e. s. tbl.; AgA ndl, fr. h. aq.; ZnA,, d.s. aq. 

Allylacetic Ac., CH,: CH.(CH,),.CO,H.—G. 0-9842 at 15°.—Unpleasant 
valerianic odor.—D. s. aq.; e. s, alc. or eth.—Gives Test 304.—No 
ppt. w. CaCl,.— Aga, ndl. fr. h. aq. 

Methylisopropylacetic Ac., Me.CHPr.CO,H.—Cf. Div. B, Sect. 1. 

n-Butyric Anhyd., (Pr.CO),.0.—G,. 0-978 at 15-5°.—For behavior on 
titration cf. p. 37. Identify by conversion into butyr-p-toluide 
(cf. p. 81) by methods indicated under anhydride of Iso-acid 
above ! 

Tetramethylenecarbonic Ac., C,H;.CO,H.—G. 1-05387°/,—D. s. aq.; 
misc. ale.—Odor penetrating, unpleasant.—Oxid. by alk. KMnO 
Br, does not add.—CaA,+5H,O, v. e. s.; Aga ppt. 

[+]Caproic Ac., Me.CHEt.CH,.CO,H.—G,. 0-930 at 15°. 

Ethyl Diacetoacetate, C,H,O,.Et.—G. 1-101 at 15°.—D. s. aq.—FeCl, » 
gives bright-red color to sol. !—‘‘ Expels acetic ac. fr. its salts.”— 
CuA,+2H,0, sky-blue ppt. w. copper acetate. 

Hexen(1)oic(6) Ac., C,H, 0,.—Ba salt, lft., e. s. aq. or ale. 

y n-Caproic Ac., Me.(CH,),.CO,H.—G. 0-9449 at 0°.—M. p. —5-2°.— 
Unpleasant odor, like valerianic acid, but fainter.—V. d. s. aq.— 
CaA,+H,0, lft. s. in 37 pt. aq. at 18-5°; AgA ppt.; ZnA,+H,O 
cryst. ppt. formed when ac. is poured into ZnAc, sol. 

Hexen(2)oic(6) Ac., C,H, ,0O,.—Still liquid. at —10°.—Ba salt alm. i. 
ale. 

Methyldiethylacetic Ac., Me.CEt,.CO,H.—Oil, alm. i. c. aq.; still liquid 
at —20°.—BaA,+5H,O, ndl. e. s. aq. 

Isobutylacetic Ac., Me,.CH.(CH,),.CO,H.—G. 0-925 at 20°.—Odor un- 
pleasant.—CaA,+5H,0O, s. aq. 

Isoamylacetic Ac., Me,.CH.(CH,);.CO,H.—G. 0-9122 at 19°.—CaA,, 
d- 8. boaq. 

Ethylpropylacetic Ac., Me.(CH,),.CHEt.CO,H.—CaA,, more s. in ¢. 
than in h. aq. 

2-Methylhexanoic(1) Ac., C;H,,,CHMe.CO,H.—Alm. i. aq.—CaA,+ 
6H,O, ndl., quickly efflorescing; c. saturated sol. becomes turbid 
on warming. 


bf 
43 





75 


76 GENUS Il; DIVic Be SECToS2. 


(ORDER I, SUBORDER I.) 








Boiling-point Neut. |LIQUID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) 
(C.°). i 


Equiv. in 50 parts of cold water. 
211-2 114 2-Methylpenten(3)-oic(5) Ac., C,H, ,O,.—Oil of unpleasant odor. 
213c. 114 2-Methylpenten(2)-oic(1) Ac.—Cf. m. p. 24-4°, Div. A, Sect. 2. 
213—4c. 56 Citraconic Anhyd., C,H,O,—G. 1-262 at 4°——M. p. +7° (tends to 
remain liq.).—(Citraconic ac. is v. s. aq., m. p. 80°.) 
214-15 114 | Pentamethylenecarbonic Ac., C,H,.CO,H.—G. 1-0385 at 25°.—M. p. 
—4° to —3°.—Odor like’ perspiration. 
215 93 | Valerianic Anhyd., (C;H,O),.0.—(Prepared fr. fusel oil.) —G.0.929?7/,. 
—Cf. Test 307. 
218 (th. 1.) 130 | Teracrytic Ac., C,H,,0,.—Unpleasant valerianic odor.—Adds Br, easily. 
219-5 144 | Dipropylacetic Ac., Pr,.CH.CO,H.—G. 0-9215°/,—D. s. aq.—CaA,+ 
2H.O,. 8. aq: 
221 130 | Act. Amylacetic Ac., (Me)(Et).CH.(CH,),.CO,H.—G. 0-9149 at 20°. 
223 130 n-Heptylic (Geannthyiie) Ac., Me.(CH,) ,.CO,H.—G. 0-9313 at 0°.— 


‘“Faint tallow-like odor.’’—CaA,+H,O, s. 110 pt. aq. at 8-5°.— 
PbA,, ppt. (lft. fr. h. aq.); ZmA, easily ‘eryst. fr. h. abs. ale., giv- 
ing prisms (dried) w. m. p. 132°; Aga, ppt., ndl. fr. h. aq. 


227c¢. 140 | Diallylacetic Ac., (C;H;),.CH.CO,H.—G. 0-9555 at 15°.—Unpleasant 
odor.—Alm. 1. aq.—Gives Test 304.—CaA,+2H,O, less s. h. 
than c. 
227 (th. 1:) 128 | Hepten(3)oic(1) Ac., Pr.CH:CH.CH,.CO,H.— Gives Test 304.— 
BaA,, 
230 107 Diethylacetic Anhyd., (Et,.CH.CO),.0.—Cf. Test 307. 
235 144 | 2-Methylhexamethylenecarbonic(1) Ac., C,H,,.CO,H.—G. 1-0079 at 
4°.—Odor unpleasant. 
237 - 5c. 144 | }{n-Caprylic Ac., Me.(CH,),.CO,H.—G. 0-91007°/,.—Lft., m. p. +16-5°. 


—S. in 400 pt. aq. at 100°; alm. i. c. aq. Cale O, ndl. v. d. 
s.c. aq.; ZnA,, scales (m. D. 136°); AgA curdy ppt. 


238-40 Diethyl Acetylmalonate, Me.CO.CH(CO,Et),.—Alc. sol. colored dark 
red by FeCl, !—Cf. Genus IV, 

240-2 154 | Cis-trans-Campholytic Ac., C,H,,0,.—G. 1.01738/,.Unsaty—Znde 
ppt. e. s. eth. 

245-6 78 | s-Diethylsuccinic Anhyd., [CO.(CHEt),.CO].0.—G. 1-0861%5/,.—wW. 


aq. gives mixture of para and anti acids which are d. s. aq.; former 
melts at 192°, latter at 129°. 


245-6 116 | + Levulinic Ac.—Cf. Div. A, Sec. 1, M. p. 33°. (If slightly impure 
usually remains liquid at ordinary temperature after fusion.) 
245-8 144 Cycloheptanecarbonic Ac., C,H,,.CO,H.—Sharp-smelling oil, remain- 


ing liq. at —20°.—CaA, (at 140°), silky ndl. fr. dil. ale. 


253-4 (th. i.) 158 | + Nonylic (Pelargonic) Ac., Me.(CH,);,,CO,H.—G. 0-9068175/,— 
Odor faintly rancid but not very unpleasant. —Leafy cryst., m. 
p. 12-5°.—BaaA,, lft. v. d. s. c. aq.— Aga, ppt., v. d. s. h. aq. 


257 [+]-Citronellic Ac., C,H,,0,—Opt. active-—Odor like Ape ac.— 
Unsat. 
264-5 150 a-Phenylpropionic (Hydratropic) Ac., Me.CHPh.CO,H.—Heavier than 


aq. and v. d. s.—BaA,+2H,0, ndl. s. aq.—AgaA, scales, e. s. h. 
aq.—Amide, m. p. 92°. 


265- 5c. 168 a-Campholenic Ac., C,,H,,0,.—G. 1-0092 at 0°.—I. aq.; e. s. ale. or | 
eth.—Yellow viscous oil w. turpentine odor! Gives Test 304. 
266-9 Phenylacetylacetone, Ph.CH,.CO.CH,.CO.Me.—Cf. IV, B. 
268-71 121 CEnanthylic Anhyd., (C,H,,0),.0.—G. 0-932 at 21°.—Cf. Test 307. 
272 178 | Ethylbenzylacetic Ac., Et.CH.C;,H,.CO,H.—Baa,, s. aq.; AgA curdy ppt. 
275-80 184 | Umbelulic Ac., C,,H mn —M. p. 21°-23°, —Ag salt cryst. fr. h. aq.— 
Faint tallowy odor. (From California laurel.) 
292 sl. d. 176 | 2, 6-Dimethyloctanon(3)-oic(8)Ac., C,,H,s0;.— Yellow oil, v. a 8. aq.; 


e.s. alc. or eth.—Br (in CHCl,) gives oily substitution product.— 
Ba salt, e. s. alc. 


___ 300-10 228 my ihentyincede Ac., C;H,,.CH(C,H,,).CO,H.—Still liq. at —10°. 





NUMBERED SPECIFIC AND SEMI-SPECIFIC TESTS 
FOR ACIDS. 


[TESTS 301-400.] 


301. Neutralization Equivalent (Neut. Eq.). 

The neutralization equivalent of an acid is the number expressing in grams the quan- 
tity of the compound required for the neutralization of one liter of normal alkali. For 
monobasic acids it is identical with the number representing the molecular weight; for 
polybasic acids a simple submultiple of this number. In the tables the neutralization 
equivalent always follows the melting- or boiling-point of an acid in the next vertical column 
to the right. Its value in this genus ranges from 45 to above 400, and is a numerical 
constant of great analytical importance. 

The determination of neutralization equivalent should be made with a portion of 
the acid which has been dried to constant weight at 105°-110°, in order to remove hygro- 
scopic moisture or water of crystallization, —the equivalents in the tables having been 
calculated for the anhydrous acids whenever these are easily obtainable. The titration 
should be performed with a pure decinormal sodium hydroxide or baryta solution, using 
phenolphthalein as the indicator, and observing all the precautions noted in the observa- 
tions on Generic Test III (p. 35). If the supply of the substance permits, it will, how- 
ever, be better to weigh out 0.200 grm. of the acid instead of 0.100 grm., and also to double 
the quantities of phenolphthalein and water or alcohol prescribed. These changes in 
quantities will not affect the “sharpness limit” demanded in Test III, but will raise the 
minimum limit of decinormal alkali consumption set for all species of the genus from 2 ce. 
to 4 ce. 

To calculate a neutralization equivalent from the results of a titration, it is only neces- 
sary to substitute the experimental data into the following formula: 


1000 X grams of acid taken 


eae ec alli consumed 5< nora ctreuetnvoralinl 


If 0.200 grm. of benzoic acid, for example, neutralized 16.41 cc. of a 0.0999 baryta 
solution, the neutralization equivalent of benzoic acid would be 
1000 < 0.200 
Be ae eee PONE 
16.41 x0.09997 122-0. 


Titrations with decinormal acid and alkali are made with such frequency in organic 
analysis that it is almost imperative that every organic laboratory should have these solu- 
tions, each with its special burette, always ready for immediate use. One of the simplest 
and most satisfactory arrangements for this purpose is shown in Fig. 2. The bottles, 
even in small private laboratories, should have a capacity of not less than three liters, 
and the labels should be inscribed with the dates of standardization as well as the titres 
of the solutions. The bottle figured in the cut is fitted for use with caustic alkali, and 
its contents are protected from carbon dioxide by the small guard-tubes A and B, 


which are packed with granulated soda-lime. The arm C supporting the burette is a 
77 


78 NUMBERED SEMI-SPECIFIC TESTS FOR ACIDS. 


strip of wood two inches wide and an inch thick, through which three circular holes 
have been bored to admit the passage of the neck of the bottle, the tube D, and 
the burette. After boring the holes the strip is sawed longitudinally through the 
middle, and the two halves are then tightly clamped in position by the long screws 
whose heads are visible in the cut. Strips of rubber, leather, or canvas should be 
wrapped around the glass surfaces at the points of 
contact to ensure a firm hold on the bottle-neck and 
burette without risk of crushing them when the screws 
are tightened. The burette is filled by suction at E, 


or, if it is preferred, by the action of a pressure-bulb 
attached at F. 


302. a-Hydroxy-acids. 

Dissolve 0.1 grm. of the acid in 100 cc. of cold 
water. Place 20 cc. of this solution in a test-tube of 
about 20 mm. diameter; add one drop of a ten-per- 
cent aqueous solution of crystallized ferric chloride, and 
mix quickly. Hold the tube over a sheet of white paper 
side by side with another of like size, containing 20 ce. 
of a cold aqueous tartaric-acid solution of exactly the 
same concentration as that of the unknown acid, and 

Z with which one drop of the same ferric-chloride solution 
ee Fee has also just been mixed. Compare the “hues” and 
: = C “tints” of the colors in the two tubes with each other, 


==> D 
* oe and with the color standard (cf. p. 232), observing the 
ms color from above. 
After a few seconds the color of the tartaric-acid 


a aa 
Ph )) 
faueieerce 








LO TS Se TS 






































solution will be a clear yellow (Y-YT1). If the hue of 

the solution of the unknown acid is nearly the same, 

——— while the intensity of its color equals or exceeds that 

=S: of the standard, the substance is very likely to be an 

: a-hydroxy-acid. If, on the other hand, the color is 

distinctly paler than the standard (i.e. lighter than 

YT1), or is a tint of yellow-orange or orange-yellow, the 

test has little significance. 

STS This test can be used only with cold solutions; for 

heat alone develops a yellowish coloration in ferric- 

chloride solutions of the concentration employed. Nearly all hydroxyl derivatives, when 

in sufficiently concentrated solution, will give a slight coloration with dilute neutral ferric 
chloride. The test is therefore valuable only when made comparatively. 

While it is not impossible that the hydroxyl group may produce identical color-effects 
in the case of some acids in which it does not occupy the alpha position with reference 
to carboxyl, in absence of any direct evidence that such acids exist, it may be assumed 
that the phenomena of this test are characteristic of the a-hydroxy-acids. Yellow colors 
approaching Tint 2 are likely to be given by almost any soluble acid. The colors given 
by the polybasic and keto-acids are much the most intense. Oxalic acid gives YT2-1— 
GYT2-1. Succinic and glutaric acids give slightly brownish colors, OYT1-2. Malonic 
acid gives no color. Pyruvic acid gives a Y-YO, and might almost be mistaken for an 
a-hydroxy-acid. Acetic acid and its homologues give a color that is YT2 or paler. 

303. Acids Losing Carbon Dioxide at 200°. 

Place 0.1 grm. of the acid in a piece of glass tubing 8 cm. long and 5 mm. in internal 
diameter, sealed at one end. Connect the open end by a bit of rubber tubing with a narrow 





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i 


RAH 
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My 
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I 
i 
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Hl 
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NUMBERED SEMI-SPECIFIC TESTS FOR ACIDS. 79 


gas delivery-tube that leads into a three-inch test-tube (‘‘weighing-tube”’) containing clear 
baryta solution. Immerse the tube holding the acid for half its length in a bath of melted 
paraffin, or the sulphuric-acid mixture of page 219, contained in a small beaker. The bath 
must have been previously heated to 200° and be held constant at this temperature during 
the experiment. Continue the heating for two minutes. Acids that lose one or more 
molecules of carbon dioxide below 200° will give a heavy precipitate of barium carbonate. 
This test is given by all acids having two or more carboxyl groups attached to the same 
carbon atom. Other acids, excepting only a few of unusual instability, do not give it. It is 
not given, for example, by oxalic, tartaric, citric, lactic, salicylic, tannic, or gallic acids, 
although none of these compounds are particularly stable substances. Whenever the reac- 
tion does take place with a polybasic acid, one product is an acid of lower basicity. Thus, 
malonic acid gives carbon dioxide and acetic acid: CH2.(CO.H),=CO,+CH;.CO.H. By 
repeating the experiment on a somewhat larger scale, and continuing the heating as long as 
carbonic acid is given off, the organic acid formed may generally be isolated and identified. 


304. Unsaturated Acids. 

Dissolve 0.1 grm. of the acid in 3 ec. of sodium-carbonate solution (the ordinary 
laboratory reagent, about 1:10). Then add, drop by drop, a one-per-cent solution of 
potassium permanganate. 

If the purple color of more than 1 cc. of the permanganate is instantly destroyed, 
and a brown precipitate of oxides of manganese appears, the acid may be unsaturated. 

The essential phenomena in this test are very uniform, and easily observed. Several 
cubic centimeters of the permanganate are usually reduced, and the reaction is practically 
instantaneous. It is unsafe, however, to draw the conclusion that every acid which shows 
this behavior must be unsaturated. Formic acid, and most phenol acids like oxybenzoic 
acid and gallic acid, behave like the unsaturated compounds; but saturated acids are, 
as a rule, very slowly attacked, if at all. 

As a confirmatory test for unsaturation in acids, Test 901 is often very useful. But as 
the addition of bromine at the multiple bonding, on which this reaction depends, takes 
place very slowly in the case of some of the double-bonded dibasic acids, the results (e.g. 
with fumaric acid) are occasionally a little difficult to interpret. Other cases in which 
unsaturated acids do’not add bromine easily are discussed by Bauer (Ber. 37, 3317), and 
Sudborough and Thomas (Soe. 97, 715). 


305. Use of Esters with Characteristic Odors. 

The odors of many volatile esters are highly characteristic, though an adequate verbal 
description of their peculiarities can seldom be given. Ethyl cinnamate and ethyl ben- 
zoate may both be said to have an agreeable, sweet, aromatic odor; yet no one who is in 
the least familiar with these compounds would be in any danger of mistaking one for the 
other. The following procedure is occasionally referred to in the tables as a simple means 
for distinguishing between acids by differences in the odors of their esters. It is most satis- 
factory when it can be followed by a duplicate comparative experiment in which the organic 
acid used is known. The result requires confirmation by other more exact methods. 

To a few centigrams of the dry acid in a test-tube, add 0.5 ce. of a mixture of one part 
of concentrated sulphuric acid and two parts of methyl or ethyl alcohol. Heat the mixture 
several minutes at about 100°, keeping the tube loosely stoppered and the upper portion 
cool. Pour off into 3-5 ec. of cold water in a watch-glass. Warm gently and note the 
odor. 

An odor is much more easily observed in the open watch-glass than in a test-tube, and 
the dilution with water removes the sharp smell of sulphurous acid or alcohol that might 
otherwise mask the more delicate odor of the ester. 


80 NUMBERED SPECIFIC TESTS FOR ACIDS. 


306. Precipitation of Metallic Salts. 

The statement in the description of any acid, that its calcium salt is insoluble in water, 
does not justify the unqualified conclusion that it will appear as a precipitate when an 
aqueous solution of the acid is mixed with one of calcium chloride; for the salt will often 
be held in solution by the hydrochloric acid, which is the second product of the reaction. 
But a precipitate may usually be expected, whenever the neutral sodium salt of an organic 
acid is mixed with an equivalent quantity of any other neutral metallic salt which by a 
metathesis could yield a compound described in the tables as “‘ insoluble.” 

In attempting to prepare an insoluble salt of an acid for analytical purposes, it is 
therefore a good general rule to start from an exactly neutral solution of its sodium salt, 
rather than from the free acid itself. To obtain such a solution quickly, a small quantity 
of the acid may be dissolved or suspended in about twenty parts of water, a trace of phe- 
nolphthalein added, and caustic-soda solution then dropped in until the first appearance 
of a pink color; or, when the acid is difficult to obtain in quantity, the solution left over 
from the determination of neutralization equivalent in Test 301 may be used, after being 
somewhat concentrated by evaporation. 

When engaged in experiments of this kind, it is well to remember that some precipitates 
which, when once separated from solution, are very insoluble, do not appear immediately 
upon mixing the reagents; also, that some of the most characteristic salts of certain acids 
with the alkali earths, manganese, and zinc are more soluble in cold than in hot water, 
and hence do not begin to precipitate until the solutions containing them are heated or 
boiled. 


307. Acid Anhydrides of Genus III. 

All these anhydrides are soluble in dilute aqueous alkali to salts of the corresponding 
acids, though in many cases solution proceeds slowly. A general method for the identifi- 
cation of such compounds is, therefore, to exactly neutralize and dissolve them, while sus- 
pended in water, by the addition of an equivalent quantity of caustic-soda solution; to 
decompose the soluble sodium salts with an exactly equivalent quantity of normal 
sulphuric or hydrochloric acid; and then, finally, to isolate and examine the liberated 
organic acid. 

A second important method is conversion into anilides or p-toluides. The anhydride 
is treated—heating above 100° for some minutes is occasionally necessary—with some- 
what more than an ‘‘equivalent’”’ weight of aniline or p-toluidine. The reaction product 
is crushed; washed with a little cold dilute acid, to remove the excess of base; and then 
purified by crystallization from hot water, dilute alcohol, or ligroin. The anilides and 
toluides are distinguished for the ease with which they can be crystallized and purified. 
The melting-points for a very large number have been determined and will be given a 
place in Vol. II of this work. 


311. Acetic, Propionic, Butyric, and Isobutyric Acids. 

Whenever these acids have to be identified 7n an aqueous solution—and this is the 
problem which in actual practice will have to be solved more frequently than any other— 
the first step should always be to exactly neutralize with caustic soda, and then evaporate 
to dryness on a water-bath. The dry residue of sodium salt, from which it is not necessary 
that the water of crystallization should be removed, is then ready for use in the following 
tests. In very careful work, the result from the “ Preliminary Test 1” should be accepted 
as final only when it is negative. If, on the contrary, it points to the probable presence 
of one of these acids, Test 2, which is trustworthy and specific, should be applied. 

1. [Preliminary Test.]|—Place 0.05 grm. of the dry salt in a three-inch test-tube. Add 
0.1 cc. of concentrated sulphuric acid, and warm over a very small flame until the odor 


NUMBERED SPECIFIC TESTS FOR ACIDS. 81 


of the vapors of the liberated organic acid can be easily recognized at the mouth of the 
tube. After noting whether the odor is simply sharp like acetic or propionic acid, or sharp 
and rancid like the butyric acids, cool; add 0.1-0.2 cc. of strong ethyl alcohol, and warm 
until vapors again begin to come off freely. Then pour into a watch-glass containing 
5 ce. of cold water and carefully observe the odor of the ester that has been formed. (Cf. 
Test 305.) This is sensibly different for the different acids; but the differences are 
not great and the odors may all be described as ethereal and fruity. That given by acetic 
acid, and closely resembled by the ester from propionic acid, is often spoken of as “refresh- 
ing and agreeable.” The test is rather delicate, and, if made comparatively, may suggest 
which of the four acids is present. More than this should not be expected from it. 

2. [Identification as Toluides.]—Mix in a dry six-inch test-tube 1.0-1.2 grms. of para- 
toluidine, and 0.3-0.4 cc. of concentrated hydrochloric acid. Add 0.4 grm. of the powdered 
sodium salt of the fatty acid. Rest the lower end of the test-tube in a circular hole 1 em. 
in diameter cut, by a cork-borer, in a piece of thick asbestos-paper or thin asbestos felt, to 
screen the side walls from overheating; and support the tube in a vertical position by a 
clamp on a lamp-stand. Boil gently over a very small gas-flame for one hour. During 
the first fifteen minutes steam should be allowed to escape slowly. After about twenty 
minutes, the water having all been removed by evaporation, the vapors of the condensing 
toluidine should be seen wetting the glass in a ring showing a clearly outlined upper margin 
and extending half way up the tube. Regulate the heat so that this appearance will 
continue unchanged to the end of the hour. 

[The following treatment of the fused mixture is designed to separate the acid-toluide, 
the desired product of the reaction (RCO.NH.C,H,), from the excess of toluidine, and from 
a dark oily resinous substance, by which it is always accompanied. MResinous residues filtered 
off in the course of this treatment should never be thrown away until it is found that the 
yield of acid-toluide will be sufficient for the purpose of identification; for unless properly 
extracted, small quantities of the resin will hold back the greater part of the toluide. The sep- 
aration depends on the solubility of the toluides and the insolubility of the resin in boiling 
weter, and on the volatility of toluidine with steam. If the directions given are carefully 
followed, the yield of pure acid-toluide will be entirely satisfactory, although never large.] 

Boil the cooled reaction product with 5 cc. of strong alcohol until nothing but white 
sodium chloride remains undissolved. Pour the solution, with stirring, into 50 ce. of hot 
water in a small beaker, and boil down quickly to 10-12 ce. Filter the boiling hot solution 
through a very small wet filter supported in a funnel that has been warmed by rapid rota- 
tion in a flame. Wash the filter with 2 cc. of boiling water. Unless the resin left on the 
filter forms only an exceedingly thin film, boil out filter and resin with 5 cc. of water, 
and filter hot into the first filtrate. Boil down the combined filtrates to a volume of about 
10 ec. Cool well with running water; shake vigorously and filter. Dissolve the pre- 
cipitate in 5 cc. of boiling water; or, if it will not dissolve in this volume of water, increase 
the quantity by successive additions of 1 cc. until all does dissolve. Filter hot through 
a very small wet filter in a hot funnel 2.5 cm. in diameter. Wash with 2 cc. of hot water. 
Cool well in running water. Shake and filter. This precipitate should be white and 
free fromresin. If yellowish, another crystallization from 5 cc. of boiling water followed 
by hot filtration will be necessary. Dry the precipitate at 100°, if the odor of the acid 
was not rancid,—otherwise at a lower temperature,—and determine its melting-point. 

Acetic Acid (properties tabulated on p. 73) gives acet-p-toluide, melting-point 
146°-7° (uncor.). The corrected melting-point of the pure compound is 148.2°. 

Propionic Acid (properties tabulated on p. 73) gives propion-p-toluide, melting- 
point 123.5°-124.5° (uncor.). 

Isobutyric Acid (properties tabulated on p. 73) gives isobutyr-p-toluide, melting 
point 104°-5° (uncor.). 


82 NUMBERED SPECIFIC TESTS FOR ACIDS. 


n-Butyric Acid (properties tabulated on p. 73) gives butyr-p-toluide, melting-point 
72.5°-73.5° (uncor.). 

By diminishing the quantities of reagents and solvents used, heating for two hours 
instead of one, and working very carefully, Test 2 may be carried out with one quarter 
of the weight of sodium salt recommended; but the yield is then so small that failures 
will sometimes occur. 

The quantity of hydrochloric acid used in a test ought never to exceed greatly the 
quantity theoretically required to combine with the sodium of the organic salt, toluidine 
hydrochloride reacting upon the toluides at high temperatures. Hence, if the quantity 
of salt taken for any experiment is less than has been directed, the hydrochloric acid must 
be diminished proportionally. A moderate excess of para-toluidine will, however, do no 
harm, and the quantity should under no circumstances be reduced to less than 0.5 grm. 

Test 2 may be used for the identification of acids containing slight admixtures of homo: 
logues. In the case of acetic acid it is still applicable when the impurity is quite con- 
siderable, if the first crop of impure acet-toluide crystals is recrystallized from hot ben- 
zene. The benzene gives at the same time a good separation both from the resin and 
from homologues. The other toluides are too soluble in benzene to be crystallized from 
it with advantage, but they may be recrystallized from a few cubic centimeters of hot 
petroelum ether, in which the resin will remain dissolved on cooling. 

Whenever it is desired to separate the acids under consideration from a dilute aqueous 
solution containing salts, neutral compounds of any description, or non-volatile acids, 
proceed as follows: Distil over into a dish containing 3 cc. of normal caustic-soda solution, 
or 0.12 to 0.14 grm. of solid caustic soda dissolved in a little water, the solution being 
colored by the addition of a little phenolphthalein. As soon as enough acid has distilled 
over to discharge the pink color, evaporate to dryness, scrape together the residue of dry 
sodium salt, and use the whole of it for Test 2. 


312. Benzoic Acid. (Properties tabulated on p. 60.) 

1. To 0.1 grm. of the acid in a dry test-tube add 0.17—-0.20 grm. of phosphorus pen- 
tachloride, and warm, stirring with a glass rod until a clear solution is obtained. Cool, 
and add, drop by drop, cooling, 1 cc. of cold water to destroy the excess of chlorides of 
phosphorus. Then add slowly 0.4-0.5 cc. of aniline. Dissolve the reaction product in 
2 to 5 cc. boiling dilute alcohol (1:1). Cool. Filter off the white crystalline precipitate; 
dry at 100°, and determine the melting-point. 

The benzanilide obtained from benzoic acid in this test is in the form of pearly-white 
scales melting at 159.5°-160.5° (uncor.). 

2. Heat in a six-inch test-tube for one-half hour 0.1 grm. of the acid, 0.5-0.7 grm. 
of para-toluidine, and two or three drops of concentrated hydrochloric acid. The tube 
must be supported by a clamp, and its bottom made to rest in a circular hole 1 em. in 
diameter, cut by a cork-borer in a piece of thick asbestos-paper which has been laid upon 
the small iron ring of a lamp-stand. Heat with a very small flame whose height is so regu- 
lated that the vapor of the boiling toluidine shall condense upon the walls of the tube for 
a distance of two to three inches from the lower end. Dissolve the reaction product in 
10 cc. of dilute alcohol (1:1). Filter hot. Cool and filter. Wash the crystalline precipi- 
tate with 5 cc. of cold water. Repeat the crystallization with the same quantity of 
solvent, and wash as before with 5 cc. of water. Dry at 100°-105° and determine the 
melting-point. 

p-Benztoluide, the product in this test, crystallizes in white or slightly yellowish 
plates melting at 155.5°-156.5° (uncor.). 


313. Cinnamic Acid. (Properties tabulated on p. 61.) 
1. Stir 0.05 grm. of the acid into 3 ce. of a cold ten-per-cent solution of potassium 





NUMBERED SPECIFIC TESTS FOR ACIDS. | 83 


permanganate on a watch-glass or in a small round-bottomed glass dish. A strong odor 
of bitter almonds (benzaldehyde) will immediately develop. 

2. Stir 0.1 grm. of the powdered acid into 3 cc. of fuming nitric acid (sp. gr. 1.48- 
1.60), contained in a small round-bottomed dish. The substance will at first dissolve, 
but within two or three minutes a considerable light-colored precipitate will separate. 
Allow to stand for 7-10 minutes. Then mix with 30 ce. of cold water and stir for a minute. 
Filter off the bulky precipitate of nitro acids and wash with 10 cc. of cold water. Transfer 
the precipitate to a test-tube and boil with 5 cc. of strong alcohol. Cool well. Shake, 
and allow to stand a few minutes to insure complete precipitation. Filter, and wash 
with 5 cc. of cold alcohol. Boil up the precipitate in a test-tube with 5 cc. of ether. Cool. 
Shake and filter. Wash the rather scanty precipitate with 5 cc. of cold ether. Dry at 
100°, and make a melting-point determination. 

' The final product in this test is para-nitrocinnamic acid. It is more or less distinctly 
crystalline, nearly white, and melts to a dark-brown liquid at 286°-287° (uncor.), after 
turning brown and beginning to soften at about 265°-270°. 

[Ortho-nitrocinnamic acid, and possibly a little nitrobenzoic acid, are also formed 
during the nitration, but they are completely removed by the treatment with alcohol 
and ether.] 


314. Color Reactions for Citric, Malic, and Tartaric Acids. 

To 0.05 grm. of the finely powdered acid in a small porcelain evaporating-dish add 
10-15 drops of a freshly prepared solution of 0.1 grm. £-naphthol in 5 cc. of pure concen- 
trated sulphuric acid. Place the dish on a boiling water-bath and remove it at intervals 
of thirty seconds to one minute for the observation of the color changes which follow one 
another in quite rapid succession. When the maximum color intensity has been reached, 
dilute cautiously with four to five volumes of water and again note all the changes that 
occur. 

Citric Acid (cf. p. 47) gives at first a pale greenish blue, soon turning to blue-green 
(BG), and finally, rather slowly on continued heating, to an wmpure green of very slight 
antensity and permanence. The color after dilution with water is similar in quality to that 
from tartaric acid, only very much paler. 

Tartaric Acid (cf. p. 48), after exhibiting a momentary pale blue-green color changes 
very rapidly to pure intense green (G), which is rather persistent, even when heated on 
the water-bath. The dilution with water causes a change to a very distinct orange-yellow 
(YO-OY). 

Malic Acid (cf. p. 43) at first gives a momentary greenish yellow (GY-Y) that 
changes rapidly to an intense yellow (Y) which is quite permanent. Dilution gives a yellow- 
orange (YO), which is distinctly more intense than the corresponding color from the two 
other acids. 

These tests were first described by Pinerua (Compt. rend. 124, 291). While not con- 
elusive unless supported by other specific tests, they are useful reactions. They are most 
satisfactory when used as “comparative tests.” 


315. Formic Acid. (Properties tabulated on p. 73.) 

Formic acid has a very sharp penetrating odor much like that of acetic acid, but 
more irritating. Like other acids of its series, aqueous solutions of its neutral sodium 
salt show reddish or orange colorations w:th ferric chloride. Unlike its homologues it 
reduces alkaline permanganate in the cold in Test 304. 

1. To 5 cc. of a 1-3 per cent aqueous solution of the acid, add one gram, or an excess; 
of powdered mercuric oxide. Warm to a temperature of 40°-50°. Close the mouth of 
the tube with the thumb and shake vigorously for about one minute. Filter off the 


84 NUMBERED SPECIFIC TESTS FOR ACIDS. 


undissolved oxide, and boil the clear filtrate for at least half a minute. A dark gray pre- 
cipitate of finely divided mercury will appear suddenly within a few seconds after boiling 
begins. HgO+CH,O,=Hg+CO,+H,0. 

2. Place at least two drops of strong acid, or 0.1 grm. of the dry sodium salt in a small 
“weighing-tube” (a narrow three-inch test-tube). Add five drops of concentrated sul- 
phuric acid and heat over a very small flame until a brisk effervescence begins. Ignite 
the escaping gas. [H,CO,=H,0+CO.] The carbon monoxide will burn at the mouth 
of the tube with a pale-blue flame for some seconds, if the heating is continued. 

316. Glutaric Acid. (Properties tabulated on p. 42.) 

In a dry test-tube fitted with a cork stopper and a 25 cm. length of glass tubing, to 
act as a return condenser, heat 0.1 grm. of the acid with 0.4—0.6 cc. of aniline at 175°- 
190° for one hour. Boil with 10 ce. dilute alcohol (1:1). Cool and filter. Wash with 
2 cc. cold dilute alcohol (1:1). Crystallize from 5 cc. boiling strong alcohol. Cool, 
shaking if no precipitate appears at once. Filter. Wash with 1 cc. cold strong alcohol. 
Recrystallize from 4 cc. boiling strong alcohol. Filter. Wash with 1 ce. cold alcohol. 
Dry at 100°, and determine the melting-point. 

The product, glutarantlide, crystallizes in white needles and melts at 221°-222°, It 
begins to sublime slightly at 214°-218°. 


317. Oxalic Acid. (Properties tabulated on p. 42.) 

1. Dissolve a few centigrams of the acid in water. Add ammonia in excess, and 
then a few drops of calcium-chloride solution. A white pulverulent precipitate of calcium 
oxalate will at once make its appearance. The precipitate is insoluble in ammonia or 
acetic acid, but dissolves readily in dilute hydrochloric acid. 

2. In a dry three-inch test-tube (small “weighing-tube”) place 0.1 grm. of the acid 
and five drops of concentrated sulphuric acid. Heat over a very small flame so as to 
obtain a brisk effervescence. Ignite the gas that issues from the tube—(a mixture of 
carbon monoxide and dioxide). The carbon monoxide will burn with a pale-blue flame 
for several seconds, if the application of heat is continued. 

3. Heat in a six-inch test-tube for fifteen minutes 0.1 grm. of the acid and 0.5-0.7 
grm, of para-toluidine. The bottom of the test-tube should be made to rest in a circular 
hole 1 cm. in diameter cut by a cork-borer through a piece of heavy asbestos-paper. The 
tube should be supported in an upright position by a clamp, and the asbestos-screen rested 
upon the small iron ring of a lamp-stand. Heat with a very small flame protected from 
drafts, and so regulated that the toluidine vapors shall be seen to condense and flow back 
along the walls of the lower third or half of the tube. Boil out the reaction product with 
10 cc. of dilute alcohol (1:1). Cool and filter. Wash the residue of oxaltoluide on the 
filter with 5 cc. of cold water. Transfer to a test-tube and boil up with 10 ce. of strong 
alcohol. Cool and filter. Wash with 2 cc. of strong alcohol. Dry at 100°-110°, and 
determine the melting-point. | 

Oxal-para-toluide crystallizes in white plates melting at 266.5°-267.5° (uncor.). 


318. The Phthalic Acids. 

The different behavior of these isomers towards heat is an important distinguishing 
characteristic. Phthalic acid melts with loss of water at 184°, giving a sublimate of thin 
flat needles of its anhydride. Isophthalic acid also melts and then sublimes; but this 
occurs above 300°, and the sublimate is the unchanged acid. Terephthalic acid sublimes 
unchanged above 300°, but without previously melting. 


Phthalic Acid. (Properties tabulated on p. 67.) 
_ 1. Mix 0.05 grm. of the powdered acid with an equal quantity of resorcin. Place 
in a dry test-tube and moisten with one drop of concentrated sulphuric acid. Stand the 


— a ee oe ee 


NUMBERED SPECIFIC TESTS FOR ACIDS. 85 


test-tube in a small beaker containing a liquid bath (cf. p. 152), that is, at a temperature 
of 160°, and heat for three minutes. Cool. Treat the fused mass with 2 cc. dilute sodium- 
hydroxide solution. Pour off into 500 cc. of cold water. The water will show a very 
intense yellow-green fluorescence due to fluorescein (cf. Test 402). The isomers of 
phthalic acid do not give this reaction, though similar colorations are given by some other 
dibasic acids, like succinic and glutaric. The test is extremely delicate. 

2. Heat in a six-inch test-tube for fifteen minutes 0.1 grm. of the acid and 0.4-0.6 ce. 
of aniline. The tube must be supported by a clamp, and its lower end rest in a circular 
hole 1 cm. in diameter cut by a cork-borer through a square piece of thick asbestos-paper 
that is supported on the iron ring of a lamp-stand. Heat with a very small flame whose 
height is so regulated that the boiling aniline vapor shall be seen to condense upon the 
walls of the tube for a distance of two or three inches from its bottom. Boil the reaction 
product with 10 cc. dilute alcohol (1:1). Cool and filter. Wash the precipitate with 
5 cc. of cold water. Recrystallize from 10 ce. of boiling strong alcohol. Cool and filter. 
Dry at 100°, and determine the melting-point. 

o-Phthalanil, the product in this test, crystallizes in white plates which melt at 204°-205°, 


Isophthalic Acid. (Properties tabulated on p. 72.) 

Mix in a dry test-tube 0.1 grm. of the acid and 0.3 grm. of phosphorus pentachloride. 
Heat cautiously over a very small flame until the mixture fuses to a clear liquid. Cool. 
Dissolve in 2 cc. of pure methyl alcohol. 

Precipitate out the dimethyl isophthalate formed, by adding 5 cc. of cold water, cool- 
ing and shaking. Filter. Wash the flocculent crystalline precipitate with 2 cc. of cold 
water. Recrystallize from 4 cc. of boiling dilute methyl alcohol (1:1). Cool well. Shake. 
Filter, and wash with 2 cc. of cold water. Press the precipitate between dry filter-paper. 
Dry at a temperature not exceeding 50°, and determine the melting-point. Dimethyl 
isophthalate melts at 64° (uncor.). It is very much more soluble in dilute methyl alcohol 
than the corresponding terephthalate. 


Terephthalic Acid. (Properties tabulated on p. 72.) 

Follow the direction given in the test for isophthalic acid, as far as the close of the 
first paragraph. Then precipitate the dimethyl ester from the methyl-alcohol solution 
by the addition of 10 cc. of cold water. Filter, and wash the precipitate with 5 ce. of 
water. Recrystallize from a boiling mixture of 4cc. strong methyl alcohol and 1 cc. of water. 
Filter off the heavy precipitate of thin, white, lustrous crystals that separates when the 
solution cools, and wash with 3 ce. of dilute methyl alcohol (1 : 1).—[Dimethyl terephthalate 
melts at 140°. This test might be successfully condueted, if it were necessary, with much 
smaller quantities of acid and reagents than are here recommended.] 


319. Salicylic Acid. (Properties tabulated on p. 64.) 

(1) Prepare the methyl ester from methyl alcohol and 0.05 grm. of the acid or one 
of its salts by the method of Test 305. 

Methyl salicylate has the agreeable odor of oil of wintergreen. There are a few rare 
phenol-acids that are said to have a somewhat similar odor; but it is one that is not given 
by the isomers of salicylic acid, or by any acid of commercial importance. 

(2) Dissolve 0.1 grm. of the acid in 5 ce. of boiling water. Add 1 ce. of nitric acid 
(sp. gr. 1.2) and boil gently for five minutes. Pour into 20 cc. of cold water. Filter off 
the precipitate. Wash with 2 cc. of cold water. Recrystallize twice—the first time from 
5 cc. of boiling water; the second time from 3 cc. Dry, and determine the melting-point. 

5-Nitrosalicylic acid, the product in this test, crystallizes in white needles which 
begin to sinter together at 220°-222°, and then melt sharply to a brown liquid at 226°- 
227° (uncor.). | 


86 NUMBERED SPECIFIC TESTS FOR ACIDS, 


[The purple coloration (RV-VR), which will be observed in a 1 : 10000 aqueous solu- 
tion of the acid while applying Generic Test IV with ferric chloride, is a simple and favorite 
reaction. It is said to be sufficiently delicate to show the presence of the acid in solutions 
containing only one part in 500,000 parts of water. It is also given by neutral solutions of 
salicylates of the alkalies, but is prevented by the presence of free acids, alkalies, or 
salts of strongly alkaline reaction, like the alkaline carbonates or borax. The isomers of 
salicylic acid do not give it. 

Calcium and barium chlorides do not give a precipitate in neutral solutions of sodium 
salicylate, even after dilution with an equal volume of alcohol, or after adding ammonia 
and warming. Sharply ignited above its melting-point, salicylic acid emits a faint odor 
of phenol.] 


320. Succinic Acid. (Properties tabulated on p. 49.) 

Place in a dry test-tube 0.1 grm. of the acid and 0.5 grm. of para-toluidine. Immerse 
the lower part of the tube in a small beaker containing one of the liquid baths mentioned 
on page 152. Insert a cork stopper fitted with a 25 cm. length of glass tubing to serve 
as a return cooler, and heat for one half hour at 200°-220°. After the tube has been 
removed from the bath and allowed to partially cool, add 10 ce. of dilute alcohol (1 : 1), 
and boil. Cool well and filter off the crystalline precipitate of succintoluide. Wash with 
2 cc. cold dilute alcohol (1:1). Crystallize from 5 cc. of boiling strong alcohol. Filter. 
Wash the crystals with 1 cc. cold strong alcohol. Dry at 100°, and take the melting-point. 

The succintoluide thus obtained forms white needles melting at 254.5°-255.5° (uncor.). 


CHAPTER VI. 
GENUS IV. PHENOLIC COMPOUNDS 


OF 
SUBORDER I, ORDER I. 
(Colorless Compounds of Carbon, Hydrogen, and Oxygen.) 


To this genus belong all the true phenols of the suborder not included in the fore- 
going genera, and many non-aromatic “enols.”’ 


GENERIC TEST IV. 


APPLY PROCEDURE 1 OF THIS TEST FIRST TO EVERY COMPOUND, SOLID OR LIQUID. 
APPLY PROCEDURE 2 TO EVERY SOLID COMPOUND THAT FAILS TO GIVE A 
COLORATION IN PROCEDURE 1; BUT NOT TO LIQUIDS. COMPOUNDS THAT 
SHOW A PHENOLIC BEHAVIOR IN THE FIRST PART OF THE TEST ARE CLASSI- 
FIED AS PHENOLS IRRESPECTIVE OF THEIR BEHAVIOR IN PROCEDURE 2. 


PROCEDURE 1. 
(The Test with Ferric Chloride.) 


Dissolve about 0.05 grm. of the substance in 1 cc. of cold water; or, if this 
should be found impossible prepare a hot saturated aqueous solution; cool; filter, 
and use 1 cc. of the cold saturated filtrate. To this solution, in a narrow three- 
inch test-tube (small weighing-tube), held in front of a sheet of white paper, add 
three drops of the ferric-chloride reagent described below,* pausing for a few seconds 
after the addition of each drop to note whether any color change occurs. If no 
coloration is noticed, repeat the test in the same way as before, except that alcohol 
is substituted for water as the solvent. 

If any coloration, transient or permanent, other than a tone of yellow or 
orange-yellow (Y or OY), is observed, the substance is probably a phenol or an 
enol. 


PROCEDURE 2. 
(The Test with Alkali.) 


a. Place 0.10 grm. of the finely powdered substance in a narrow three-inch test- 
tube with 1 cc. of cold water, and ascertain by shaking and stirring whether it will 
dissolve. If it dissolves completely in the cold, and gave no color with ferric chloride 
in Procedure 1, it is not a phenol. 


* The Ferric-chloride Reagent.—Prepare the reagent as required for use by diluting three 
drops of the 10 per cent stock solution of ferric chloride with 1 cc. of water. 
87 


88 PHENOLIC COMPOUNDS. 


b. If the substance did not dissolve appreciably in experiment a, add 1 cc. of a 
cold aqueous sodium-hydroxide solution (1:10) to the mixture. Shake or stir 
well for about one minute, and notice whether solution is effected, and whether 
any strong coloration is produced. If the compound now dissolves completely, 
or if it dissolves completely after diluting the alkaline mixture with an additional 
cubic centimeter of cold water, the compound should be sought among the phenols. 
The appearance of any pronounced coloration in the alkaline solution, also shows 
the compound to be a phenol, though most of the phenols give colorless solutions 
in alkali. 

If a considerable part of the substance, though not all, dissolves in experi- 
ment a, add a little more of it to the solution, so that an undissolved residue of about 
0.10 grm. shall remain. Treat this mixture with sodium hydroxide just as directed in 
the last paragraph, except that the subsequent dilution with water should be omitted 
in this case, unless a change in the appearance of the powder should indicate strongly 
that the formation of a sodium salt insoluble in concentrated alkali has taken 
place. ‘The phenomena observed are to be interpreted as in the last paragraph. 


OBSERVATIONS ON GENERIC TEST IV. 


In ‘‘the test with ferrie chloride” yellow and orange-yellow colorations have 
to be disregarded, because tones of these hues are produced by many polyatomic 
alcohols belonging to subsequent genera. A strong yellow also appears whenever 
alcohol is substituted for water as the solvent. Fortunately the colorations given 
by phenols, although varying widely in hue, intensity, and permanence, are not 
very often yellow, or either of the two adjacent hues in the color standard. The 
colorations characteristic of some phenols appear in extremely dilute solutions, 
others only in concentrated solutions. Some remain unchanged in quality for 
many hours; others appear and disappear within a second. A trifling excess of 
the reagent is sometimes sufficient to destroy the color; in other cases it is beneficial 
or necessary. It is for this reason, that it is desirable to observe the color after the 
addition of each drop of the chloride. The ferric-chloride test is applicable to cold 
solutions only. For further information concerning this reaction see numbered 
Tests 302 and 401. 

In ‘‘the test with alkali ”’ several distinct principles are involved. The first 
and most important of these is, that, with the exception of some polyatomic phenols 
like resorcin and pyrogallol, the species of this genus as a class are not ‘‘ easily 
soluble” in cold water, although they do dissolve readily in cold sodium-hydroxide 
solutions of certain concentrations. For the larger number of species a ‘‘ normal” 
concentration of the alkali has been found to be the best. But since the sodium 
salts of some phenols (e.g. sodium-methy] salicylate) are much less soluble in strong 
caustic soda than in water, they occasionally appear as precipitates even when 
the alkali used is only normal. It is to provide for this contingency that it is directed 
to dilute with about one volume of water whenever a precipitate (an insoluble 
sodium phenolate) is found to form. The use of a weaker alkali at the start is not 
advisable, because the salts of many phenols are so completely hydrolyzed in solution, 
unless a considerable excess of alkali is present, that their solubility in decinormal 
soda may appear to be no greater than in pure water. Finally, it should be men- 


PHENOLIC COMPOUNDS 89 


tioned that a few compounds having phenolic structure will not dissolve unless 
the alkali is much stronger than normal. But their number is so small that it has 
been considered better to treat them as exceptions than to complicate the test for 
the sake of assuring them a position with the other phenols. 

The production of a colored solution in the test with alkali is not a general 
reaction of the phenols, but whenever a coloration does appear at this point, or in 
the titration in Test III, in the examination of an unknown substance, it is a very 
significant phenomenon, and is alone sufficient to indicate that the body should be 
sought among the phenols. The colors are sometimes very brilliant, as with the 
phthaleins, but often yellow, and sometimes dark brown, appearing gradually on 
stirring. Brown colorations are characteristic of phenols like pyrogallol, whose 
alkaline solutions are rapidly oxidized by the absorption of atmospheric oxygen. 

It is necessary to restrict ‘‘the test with alkali” to solid phenols, because it 
has been found that a considerable number of liquid species in Genus V and VI 
(e.g. diethyl succinate), which react neutral in Test III with very dilute alkali, 
are saponified by short shaking with a 1:20 aqueous soda solution. Since the 
liquid phenols, so far as is certainly known, all give colorations with ferric chloride, 
this limitation placed on the application of the alkali test is accompanied by no 
serious disadvantages. 


General Physical and Chemical Characteristics of the Phenols and Enols. 

Many of the phenols, like ordinary phenol, eugenol, and methyl salicylate, possess 
intense and characteristic odors and tastes; but many solid species are odorless and taste- 
less. All except a few of the simpler phenols, such as ordinary phenol, resorcin, and 
pyrogallol, are nearly insoluble in cold water, though soluble in solutions of the caustic 
alkalies. All the water-soluble species either give colorations in the test with ferric chlo- 
ride, or else solutions in dilute sodium hydroxide that rapidly turn brown through oxida- 
tion upon exposure to the air. In alkaline solution many phenols reduce potassium per- 
manganate in the cold in Test 304, and a smaller number, including many of the polyatomic 
phenols, reduce metallic silver from Tollen’s reagent in Test 101. The phenols are as a 
rule readily soluble in cold concentrated sulphuric acid, being very easily sulphonated, 
and are not reprecipitated upon dilution with water. In Test VIII they evolve hydrogen 
when treated with sodium, and are sometimes acetylated in the treatment with acetic 
anhydride. The color reactions of the phenols are numerous. Those depending upon: 
fusion with phthalic anhydride (cf. Test 402), treatment with sulphuric acid containing 
oxides of nitrogen, or with aromatic diazonium salts, all have analytical application. 
Colorations obtained with ferric chloride, as in Test IV, have been described for about half 
the solid species mentioned in this volume, and for nearly every liquid species. These color- 
ations are ascribed to the formation of unstable iron salts. Some phenols, like e-naphthol, 
whose dilute aqueous solutions are little or not at all colored by ferric chloride, are oxidized 
by it, and then separate from the solutions as precipitates of insoluble condensation prod- 
ucts (like dinaphthol). A portion of the aromatic hydrogen in phenols is very easily 
substituted by halogens or by nitro groups, poly-halogen, or poly-nitro derivatives being 
formed. Even very dilute aqueous phenol solutions consequently give precipitates upon 
treatment with an excess of bromine water (cf. Test 414-3). Test 901 may also be applied 
when evidence as to ease of substitution by bromine is desired. The nitro derivatives are 
readily prepared on the small scale, and are very often useful in completing identifications 
(cf. Tests 414-(2), 415, 418-(2), and 419). A fev’ phenols, like guiacol (cf. p. 91), give 
characteristic crystalline derivatives with picric acid. 


90 PHENOLIC COMPOUNDS. 


One of the most important reactions of the enols is their behavior upon saponifica- 
tion. The saponification may be conducted, and the saponification products identified, 
by the method of Part 2 of Test V, as described on pp. 113 et seg. The following are 
examples of such reactions: 


CH,.CO.CH,.CO.CH,, (or, CH,.C(OH): CH.CH,) +KOH=CH,.CO.CH, + CH,.CO,K. 


(Acetyl acetone) (Acetone) (Potassium acetate) 
CH,.CO.CH,.CO,Et, (or, CH,.C(OH): CH.CO,Et) + 2KOH=K,CO, + CH,.CO.CH, + EtOH. 
(Acetoacetic ether) (Acetone) (Alcohol) 


The names usually applied to the enols in the tables of this volume, and in the illus- 
trations here given, are those properly belonging to the ketones with the corresponding 
desmotropic formule. This keto nomenclature, while open to criticism, is used, because, 
besides being probably the one in more general use at the time of writing, it also more 
quickly suggests the names of the saponification products that are to be expected. The 
enols, like the phenols, are soluble in cold dilute alkalies, give colorations with ferric 
chloride, and are attacked by sodium or bromine. When shaken with a saturated solution 
of copper acetate in water or dilute alcohol, some enols give precipitates of yore and 
characteristic blue or green copper salts. 


COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I]. 
GENUS IV, PHENOLIC COMPOUNDS. 


DIVISION A,—SOLID PHENOLIC COMPOUNDS. 


eee eon PHENOLIC COMPOUNDS.—OColorless and Solid. 
26 211-5c. J 1, 3-Xylenol(4), Me,.C,H,.0H.—V. d. s. aq.; miscible w. 


alc. or eth.—In Test 401 w. FeCl,, the 1% alc. sol. gives a 
GB color, very quickly fading through G to YT2, while 
the aq. sol. (1:100) gives a BV color, which fades in 2 min, 


to a white turbidity. 


26 228 m-Propylphenol, Pr.C,H,.OH.—V. d. s. aq.—Aq. sol. pale blue 


w. FeCl,; alc. sol. green. 
30 190-8 t o-Cresol, Me.C,H,.OH.—1% aq. sol. w. FeCl, in Test 401 
gives a VB color on mixing, changing to Y in 5 min. and 
later to a turbid brown —The picrate, prepared by mixing 


a sol. of the cresol in a little 50% alc. with a concentrated 
solution of picric acid in 50% alc., forms orange-yellow 
ndl. w. m. p. 88° (m- and p-cresols give no picrates).— 


Unlike phenol, not dissolved by 5 pt. conc. NH,OH! 


31-2 205 + Guiacol, o-MeO.C,H,.OH.—S. in 60 vols. aq. at 15°.—The 
1% aq. sol. gives w. FeCl, in Test 401 a ROR color which 


slowly fades, the sol. becoming turbid. The 1% alec. sol. 


gives a GB w. FeCl,, which very rapidly fades to a YT2.— 
The alkaline sol. fr. the fusion w. phthalic anhydride in 
Test 402 has a VB-BV color, and an absorption spectrum 


not easily distinguishable from that of thymol (IV, A, 


m. p 49-6°)—7To a mixture of 0-1 grm. guiacol and 
1 ec. aq., add a hot sol. of 0-2 grm. picric acid in 5 cc. aq.; 
shake well and allow to cool slowly. A brilliant O-YO cryst. 
ppt. of the picrate compound, w. m. p. 86°, appears within 


@ minute or two! 


35 Diacetylbenzoyl Methane, Ph.CO.CH.(COMe),.—E. s. alc.; s. 
w. yellow color in Na,CO,;.—Ale. sol. blood-red w. FeCl,.— 
Cu salt dark blue tbl. w. m. p. 224°-5°, s. CHCl;.—Saponi- 
fication by Test V-2 gives acetophenone and acetic ac. 


(Tests 712 and 311). 


36 201-8 } p-Cresol, Me.C,H,.OH.—Is not dissolved by 5 pt. cone. 


on mixing; the sol. then finally becomes turbid. 
40-1 250 (560 mm.)| o-Oxybenzophenone, Ph.CO.C,H,.OH.—M. p. oxime 133°-4°, 


NH,OH.—Aq. sol. (1:100) in Test 401a gives BVT1-BT1-2 


42-5 172-3 (12 mm.)| + Phenyl Salicylate (Salol), o-HO.C,H,.CO,Ph.—Odor faintly 





414). 


aromatic.—Alm. 1. h. aq. (dif. fr. phenol); e. s. alc. or eth.— 
Dil. ale. sol. colored violet-red w. FeCl,.—Saponification 
by Test V—2 gives salicylic acid and phenol (Tests 319 and 


42-5-3 183 + Phenol, C,H;.OH.—S. in 15 pt. aq. at 16°; alm. i. Na,CO,; 
miscible w. alc. or eth. Is dissolved by less than 5 pt. 
cone. ammonia (dif. fr. cresols)—An aq. sol. (1:100) w. 
FeCl, (Test 401) gives a violet color (V), permanent for 


more than 15 min.—Identify by Test 414! 


43 Ethyl Benzoylpyruvate, Ph.CO.CH,.CO.CO,Et.—Dec. on dist.— 
Pr. fr. lgr., e. s. ale—Alec. sol. blood-red w. FeCl,—Saponifi- 
cation by Test V—2 gives acetophenone (Test 712), sodium 


oxalate, and ethyl alcohol. 


91 





92 


GENUS. 1V,, DIV, A. 


(ORDER I, SUBORDER I.) 





Melting-point 
(C.2%, 





46 
47 
49 


49 


49-6 


50 


51 


51-2 


53 


57 


59-60 


60 


60-1 


61 


63-6 


65 








Boiling-point 
CORA. 


218-5 
239d. 


211-2 


231-8 


251-2 


253 


243 


239 
330-40d. 


260-2 


229¢ 


225c. 


PHENOLIC COMPOUNDS.—Colorless and Solid. 


p-Ethylphenol, Et.C,H,.OH.—V. s. alc. or eth.—Aq. sol. gray- 


blue w. FeCl, Warmed w. P.O, gives phenol and ethylene. 


Isohomopyrocatechin, Me.C,H,.(OH),(1, 2, 3).— E. s. aq., alc., 
or eth.—Aq. sol. gives a transient green w. FeCl,. 

1, 3-Xylenol(2), Me,.C,H;.OH.—S. h. aq.—Tribrom-derivative, 
in opeelio-. 

Diacetylacetone, CO.(CH,.COMe),.—Decomposes spontaneously, 
—Lustrous lft. e. s. eth. or h. alc.; sol. in alkalies w. yellow 
color! Gives dark-red color w. FeCl,.—Gives a leaf-green 
Cu salt and light-yellow Ba salt i. aq—With NH, gives 
lutidone. 

{+ Thymol, Me.C,H;.(Me,CH)(OH)(1, 4, 3).—Strong odor of 
thyme !—S. at 15° in 1200 pt. aq., or in 900 pt. at 100°.— 
Gives no color w. FeCl, except in cone. ale. sol. (1:2), 
when a trace of the very dil. reagent gives a transient 
green color (G). (Dif. fr. guiacol.)—Test 402 w. phthalic 
anhyd. is very striking though similar to that given by 
guiacol, The fused mass, which has a very intense VR-R 
color, dissolves to an intense blue (B) in dilute NaOH. 
This sol. shows an absorption band, when viewed through 
the spectroscope, extending fr. E to the orange. It narrows 
on cautious dilution until it finally appears as a thick line 
almost exactly at D!—Identify by Test 419! 

Paénol, Me.CO.C,H,OH.OMe.—Ndl. es. alc. or eth.; vol. w. 
st.—Alc. sol. colored dark red-violet by FeCl,.—Oxime, 
ndl., e. s. ale.; d.s. aq. 

Homopyrocatechin, Me.C,H;.(OH).(1, 3, 4). — V. s. aq. ale. or 
eth.— W. FeCl, gives green color, which changes to red- 
violet w. Na,CO,—Reduces AgNO, or Fehling’s sol. 


Pyrogalloldimethylether, HO.C,H..(OMe),.—FeCl, gives céru- 
lignon (s. in conc. H,SO, w. intense corn-flower color).— 
Conc. HCl at 100° gives pyrogallol. 


Hydroquinone Methyl Ether, p-HO.C,H,.OMe.—Not vol. w. 
st.—E. s. c. bz.—Reduces h. ammon. Ag. sol. 

Iridol, Me.C ,H,.(OMe),(OH)(3, 4, 5, 1).—E. s. alc., eth., or bz. 

Dioxybenzophenone, (C,H,OH),.CO.—Pale-yellow pr. fr. lgr.; 
alm. i. aq.; v. 8s. ale. or eth.; s. in K,CO; sol., but ppt’d by 
CO,.—Dil. alc. sol. colored brown-red by FeCl;—Warming 
w. conc, H,SO, or boiling w. KOH sol. gives carbonyldi- 
phenyleneoxide, i. aq.; m. p. 173°-4°. 

1,2 (af)-Hydronaphthoquinone, C,)H,.(OH),. — Silvery Ift., 
s. in NaOH w. yellow color, which changes to an intense 
green.—Diacetate melts at 105°. 


Benzoylacetone, Ph.CO.CH,.COMe.—D. s. c. aq.; v.s. ale. or 
eth.; e. s. NaOH; d. s. Na,CO,; i. NaHCO,.—Intense 
red color w. FeCl,!—Saponification by Test V-—2 gives 
acetophenone (Test 712).—Cu salt, pale-green ppt. by 
CuAc, fr. dil. alc. sol.! Ag salt i. ppt. 


p-Isopropylphenol, Me,.CH.C,H,.OH.—Aq. sol. becomes pale 
blue w. FeCl,; alc. sol. green. 

Dioxytoluene, Me.C,H;.(OH).(1, 2, 6). — E. s. aq. or ale.—W. 
Ca(OCl), quickly turns to a fuchsine-red color that changes 
to yellowish brown. 


t 1, 2-Xylenol(4), Me,.C,H,.0H.—Long ndl. fr. h. aqg.—Odor 
like phenol. Cold saturated aq. sol. becomes B on mixing 
with FeCl, (Test 401); the color rapidly fades, however, and 
is replaced by a white turbidity.—Tribrom-derivative 
melts at 169°. 


te 
ea ee 


a 


Melting-point Boiling-point 
(C.*). (C2), 


66 246-7 


64 or 68 219-5 
67 
68-9 219-5c. 
71-2 234-5 
73-4 
| 
| 
74.5 211-5 (th. i.) 
15 218¢. 
76-5 
79 262 
79-80 
81 
81 a. 200 
80-5 
| - 84 
84 abt. 325 
86° 
86 266 (th. i.) 








GENUS IV, DIV. A. 93 


(ORDER I, SUBORDER I.) 


a ee 


PHENOLIC COMPOUNDS.—Colorless and Solid. 





Hydroquinone Ethyl Ether, p-HO.C,H,.OEt.—Thin lft.e.s. h. aq. 
oreth:; d.s..c. aq. 


1, 3-Xylenol(5), Me,.C,H,.OH.—V. d.s. ec. NaOH.—No color w. 
FeCl,;.-M. p. of tribrom-derivative 162-5°. 


m-Oxybenzyl Alc., HO.C,H,.CH,OH.—Cryst., e. s. alc., eth., or 
h. aqg.; d. s. CHCl,—Aq. sol. gives violet-blue color w. a 
little FeCl,. 


Mesitol, Me,.C,H,.OH(1, 3, 5, 2).—V. s. ale. or eth.; i. NH,OH 
or Na,CO,.—No color w. FeCl. 


Pseudocumenol, C,H,.(Me;)(OH)(1, 2, 4, 5).—Alm. i. c. aq.; Vv. 
s. ale. or eth.—No color w. FeCl,.—Very vol. w. st.—Acetic 
ac. sol. with Br gives Br deriv. m. p. 35°. 


Coniferyl Alc., MeO.C,H,:(OH)(C,H,.OH).(3, 4, 1).—D.s. h. aq.; 
e. s. eth.; s. alkalies—Dil. mineral acids change quickly to 
amorphous isomer, alm. i. eth—Na amalgam reduces to 
eugenol, Div. B, b. p. 247°.—CrO, mixture oxid. to vanil- 
line, ete. 


I, 4-Xylenol(2), Me,.C,H;.0H.—Odor like phenol.—Gives no 
pronounced color reac. w. FeCl, in aq. or alc. ! 


1, 2-Xylenol(3), Me,.C,H,.0H.—Odor like phenol.—Aq. sol. 
blue w. FeCl, !—M. p. of tribrom-derivative 184° (ndl. fr. alc.). 


Diethyl Ketipate, EtCO,.CH,.CO.CH,.CO,Et.—Flat pr. fr. ale.— 
I. c. aq., e. s. eth.—Gives intense-red color w. FeCl, Boil- 
ing w. dil. H,SO, gives diacetyl !—Substitutes Br, easily.— 
The free acid is unstable. 


Pyrogalloldiethylether, HO.C,H;.(OEt),.—V. 8. ¢. bac G 
dil. ale-—Vol. w. st. 


Propylpyrogallol, Pr.C,H,.(OH),(1, 3, 4, 5).—V. s. aq., alc. or 
eth.—Aq. sol. indigo-blue w. FeSQ,. 


I, 2, 3-Irimethylphenol(5), Me;.C,H,.OH.—No color w. FeCl. 


Dibenzoylmethane, CH,.(COPh),.—Tbl. fr. methyl alc.; e.s. ale. 
or eth.; i. Na,CO,; v. e. s. NaOH.—Ale. sol. intense red- 
violet w. FeCl, !--Monobrom-derivative formed fr. 1-8 grm. 
Br and 2-24 grm. substance, each dissolved in 3 pt. CHCl, at 
0°, (silky ndl.mijp, 93"): 

(a)-Dibenzoylacetone, (PhCO),.C: COH.Me.—Pr. fr. lgr.; dec. at 
270°.—Sol. in Na,CO, w. yellow color.—Ale. sol. blood-red 
w. FeCl;.—Quite a strong acid.—Heated for 1 hour at 85° 
gives (@)-dibenzoyl acetone of m. p. 107°-10°, 1. in Na,CO, 
sol., and giving no color in alc. sol. w. FeCl. 

Dipyrocatechin,[C,H,.(OH),],..—Ndl.—Sbl.— Unstable.—Aq. sol. 
pale green w. FeCl,, becoming dark blue w. a little Na,CO3. 

p-Benzylphenol, Ph.CH,.C,H,.OH.—Cryst. fr. ale_—S. in NaOH, 
but not in NH,OH.—Dist. w. P,O, gives benzene, anthracene, 
and phenol. (Tests 913, 912, and 414.)—Dibrom-derivative. 
fr. excess of Br in CS, sol., m. p. 175°. 

+ Saligenin, o-HO.C,H,.CH,.OH.—Rhombic tbl.—Sbl. fr. 100° 
—HE. s. c. aqg.; v. 8. h. aq.; v.s. alc. or eth.—Test 401 w. 3 
0:5% alc. sol. and FeCl, gives a RV color, soon changing to 
YOT,.—The powder stirred w. a little conc. H,SO, gives a 
red color (RT1-VRT1).—Boiled for a short time w. 5 pts. 
aniline gives oxybenzyl-aniline, m. p. 108°; ndl. fr. ale. 

I, 2, 3-letramethy!phenol (4), Me,.C,H.OH.—E. s. alc. or eth.— 
Gives no color w. FeC],. 


94 GENUS IV, DIV. A, 


(ORDER I, SUBORDER I,) 





Motte pone oars’ ae oh PHENOLIC COMPOUNDS.—Colorless and Solid. 





88 } Diethyl Diacetylsuccinate, C,H,O,.Et,.—TDbL, e. s. alc. or eth. 
—Sat. aq. sol. w. FeCl, gives, in Test 401, a very pale but 
rather permanent violet-red (VRT2).—T To 5 cgrms. ester 
in a test-tube add 1 cc. conc. NH,OH, 1 ce. glacial acetic 
acid and 10 cc. dilute H,SO,. Place a pine splinter in the 
mixture and boil for 2 min.—The splinter becomes colored 
deep red (pyrrol reaction) !—Saponification gives acetonyl- 
acetone, C,H,OH, and COQ,. 


89 2-Methylnaphthol(1), Me.C,,H,.OH.—Ndl. fr. aq—Gives white 
ppt. w. FeCl,; green ppt. w. Ca(OCl),_Ignition w. Zn dust 
gives -methylnaphthalene. 


seer | er 


92 2-Methylnaphthol(4), Me.C,,H,.OH.—Gives same reactions as 
preceding, except that Zn dust gives a-methylnaphthalene. 
92-3 255 p-Isoamylphenol, C,H,,.C,H,.OH.—Ndl. fr. h. aq. 
93 250d. p-Anol, Me.CH: CH.C,H,.0H.—S. in alkalies—Exposure to air 
or h. dil. acids gives a brown. oil. 
94 278-80 { a-Naphthol, C,,H;.OH.—Monoclinic.—Odor phenolic.—D. s. 


h. aqa@oi-c. aq. ; e. s. alc., eth., bz., or alkalies —Aq. sol. 
gives scanty white ppt. w. FeCl,. Identify by Test 412! 


95 Pyrogallol Ethyl Ether, (OH),.C,H,.OEt.—Ndl. vol. w. st.—S. 
c.aq.; e. s. h. aq.; v. d.s. c. bz.—Gives blue-violet color w. 
FesO,. 
95 230-1 (th. i.) | Trimethylphenol, C,H,.(Me,)(OH)(1, 2, 4, 6). 
95-7 Ethyl Oxalylacetate, CO,H.CO.CH,.CO,Et.—FeCl, + aq. sol. gives 
deep-red color. 
96-7 $-Hydrojuglon, C,H. (OH),.—Silvery 6-sided ndl. fr. ale.—S. 


1000 pt. c. aq.; d.s. ale. or eth.; e. s. CHCl, and bz.—Gives 
an intense-yellow color w. N aOH, changing to red.—Boiled 
w. FeCl, gives juglon. 

98 Benzocotoin, C,;H,,0,.— Pale-yellow ndL., e. s. eth. or dil. NaOH. 
—FeCl, gives dark-brown’ color.—Ammon. sol. gives amor- 
phous yellow ppt. w. PbAc,. 


99 237 p-tert.-Butylphenol, Me,.C.C,H,.OH.—Ndl. fr. aq.—Heated w. 
P.O, gives isobutylene and phenol. 
99 o-Oxyhydroanthranol, C,,H,.0,.— Yellowish lft. fr. ale.—S. ale. 


or eth.—The alc. sol. is colored green by FeCl,.—Solutions 
show a pronounced green-yellow fluorescence. 


103 325 sl. d. Methyl Oxynaphthyl Ketone, Me.CO.C,,H,.OH.—6-sided pale- 
green pr. fr. bz.; i. aq., d. s. alc.; s. alkalies, but ppt’d by 
CO,.—Oxime, m. p- 168°-9°, 

103-4 267-70 1, 2-Dioxytoluene(4), (OH),.C,H;.Me.—HE. s. aq., alc., or eth.; d. 
s. bz.—Aq. sol. colored green-blue by FeCl,; gives ppts. Ww. 
Br or PbAc,; gives yellow color w. Ca(OCl), sol.—Phthalic 
anhyd. fusion (Test 402) gives a fluorescein. 


104 240-5 + Pyrocatechin, o-C,H,.(OH),.—Lft. fr. bz.; e. s. aq., ale., or 
eth.; s. c. bz. (Separation fr. hydroquinone.)—Aq. sol. 
(1:250) gives w. FeCl, a green (G) color, which, on addition 
of Na,CO,, changes to R, becoming OR within 15 min. !— 
Alkaline sol. browns in the air.—PbAc, gives white ppt. 
(dif. fr. hydroquinone).—Easily reduces sol. of noble metals 
and Fehling’s sol. on warming.—Apply Test 416! 

105 Homosaligenin, Me.C,H;.(CH,OH)(OH)(1, 2, 4).—Lft. s. 15 pt. 

ec. aq.—Sol. gives deep-blue color w. FeCl,.—Dec. by heat- 

ing w. dil. HCl to i. homosaliretin, m. p. 200°-5°. 

104-6 Dihydroresorcin, C,H,O,.—Pr. e. s. aq. or ale.; v. d. s. abs. eth. 

—Aq. sol. reacts strongly acid.— Aq. sol gives intense 

violet color with FeCl,. Reduces Ag sol.—Gives a phenyl- 

hydrazone w. m. p. 176° ; 








Melting-point Boiling-point 
CC). (ay: 


105-6 298 





106-5-108 287-90 
108 
108-9 
110 
110 
112 
114 255 
115 fd: 
115 295-300 
116 276-5 
116 297-8 
116 
117 227-8 (th. i.) 
117 249-50c. 
120 
120-1 
120-1 


GENUS IV, DIV. A. 95 


(ORDER I, SUBORDER I.) 





PHENOLIC COMPOUNDS.—Colorless and Solid. 





Dimethylapionol, C,H,.(OH),(OMe),(1, 2, 3, 4).—S. h. aq., ale., 
eth., bz., and alkalies. 

+ Orcin, Me.C,H;.(OH).(1, 3, 5).—Cryst. w. 1H,O (m. p. 58°).— 
Sweet taste.—E. s. aq., alc., or eth.; d.s. CHC],—A 1% aq. 
sol. gives a VBT1I-BVT1 color w. FeCl, in Test 401, which 
slowly fades to a light tint of the same hue.—Reduces am- 
mon. Ag sol.—Sol. in ammonia absorbs O from air, becoming 
red.—br aq. ppts. tribrom-derivative (ndl. fr. dil. ale., m. p. 
98°).—f Bring to a boil a sol. of 5 cgrm. orcin in 5 cc. of a1% 
NaOH sol. to which 5 drops of CHCl, have been added. An 
O-OR color is produced. Dilute the solution to 50 cc. and 
view with a black background. An intense YG fluorescence 
appears !—The phthalic anhyd. fusion (Test 402) gives a pure 
OR solution. 


I, 2, 3-letramethylphenol(5), Me,.C,;H.OH.—Alc, sol. becomes 
yellow-green w. FeCl). 


Phloridzin.—Cf. m. p. abt. 170°, at which temp. it remelts after 
losing aq. 

Ethyl Isocarbopyrotritarate. — Alc. sol. blue w. FeCl,. — Cf. 
Genus III (A, 2). 


p-Oxybenzyl Alc., HO.C,H,.CH,.OH.—Fine ndl., e. s. aq., alc., 
or eth.—Sol. in conc. H,SO, is red-violet. 


Phenanthrol, C,,H,.OH.—Lft. w. blue fluorescence.—D. s. aq.; 
e. s. alc. or eth 


Pentamethylphloroglucin, C,,H,,0,—E. s. in sol. of NaOH or 
Na,CO,.—Reduces KMnO, immediately. Abs. methyl alc. 
sol. with Br gives Br deriv., ndl., m. p. 75°-6°. 

Vanillyl Alc., C,H,.(Me0O)(OH)(CH,OH),(3:4:1).—Ndl. E. s. 
ale., eth., or warm aq.—5S. in conc. H,SO, w. red-violet color. 
—Gentle oxidation w. a little CrO, mixture gives vanilline 
(odor like vanilla) ! 


Acetovanillon, MeO.C,H,.OH.COMe.—Pr. s. in 200 pt. c. aq.— 
Cu salt a yellowish-green ppt.—Oxime melts at 95°. 

+ Resorcin, m-C,H,.(OH),.—Tbl. fr. aq., alc., or eth.—Taste 
sweet.—V. s. c. aq., alc., or eth.; 1. CHCl, or CS,—A 1% aq. 
sol. gives a strong clear BV with FeCl, (Test 401), permanent 
for more than 15 min.—Identify by Test 418! 


Ethyl p-Oxybenzoate, HO.C,H,.CO,Et.—Saponification by Test 
V-2 gives p-oxybenzoic ac. and C,H,OH. 

m-Oxybenzophenone, Ph.CO.C,H,.OH.—Lft. e. s. ale. or eth.— 
Gives two oximes w. m. p. 76° and 126°; fusion of first gives 
second. 

Pyromeconic Ac., C,H,O;.—Sbl. at 100°.—4-sided pr. fr. h. aq. 
—V.s. ale., CHCl,, and h. aq.—Gives a cherry-red color w. 
FeCl,.—Boiling w. alkalies gives formic ac. and CO,.—Salts 
very unstable. 


I, 2, 4-letramethylphenol(5), Me,.C,H.OH.—Flat pr. fr. ale.— 
E. vol. w. st. 

2, 6-Dioxy-1, 3-xylol, Me,.C,H,.(OH),.—S. aq.; v.s. ale. or eth, 
—Aq. sol. reddish w. FeCl. 

I, 3-Trioxynaphthalene, C,,H,.(OH);.—Sbl. in scales.—V. s. eth., 
CHCI,, or bz. 

Oxalyldiacetone, C,H,0.CH,.CO.CO.CH,.COMe.—Cryst. d. s. aq.; 
s alc., eth., or NaOH(Na comp. yellow).—Alec. sol. is col- 
ored dark brownish-red by FeCl,. 


saa ne ete et ee ca eee 














a ric re 





p-Diphenolethane, Me.CH.(C,H,OH),.—Cryst. fr. bz.; i. lgr.— 
_ Aq. sol. gives yellow-brown ppt. w. FeCl,.—Gives Ag mirror 


{ @-Naphthol, C,,H,.OH.—D. s. h. aq.; e. s. ale., eth., or bz.— 
FeCl, gives a white opalescence w. the c. aq. sol.—Identify 





Sbl. partially. — V. s. 
Aq. sol. w. FeCl, 
Sol. in NaOH is blue-green, soon 
turning brown.—Boiled w. aniline gives compound (lft. fr. 








Cubebin, CH,.0,.C,H,.C;H,OH.—Nadl., alm. i. aq.; d. s. ale.; s, 
eth—Conc. H,SO, quickly produces a purple-red color.— 


Diethyl Succinylosuccinate, C,H,O,.Et,.—Pale-greenish cryst. 
w. bluish fluorescence fr. eth.; v. d. s. h. aq.—FeCl, colors 
alc. sol. deep cherry-red.—The sol. in NaOH is deep yellow. 


Ndl. or tbl.—Sbl.—S. e. 
aq.; e. s. ale—FeCl, gives cherry-red color w. aq. sol.— 
Fusion w. KOH gives formic and butyric acids—BaA-+ 





Methylpyrogallol, CH,.C,H,(OH);.—Sbl. in ndl.—W. FeSO, 


Diketohydrinden, C,H,:(CO),:CH,.—Cryst. fr. lgr.; v. d.s. ce. 
aq.; e. s. h. ale. or bz. SS. w. intense yellow color in dil. 
NaOH or Na,CO,!—Boiled w. aq. or alkali gives an acidic 
body, m. p. 206°-8°, whose alkaline salts are intensely red- 


+ Pyrogallol, C,H,.(0H),(1, 2, 3).—V. s. ¢. aq.; s. ale. or eth.— 
Taste bitter (poisonous).—Alkaline sol. absorbs O rapidly. 
turning brown.—A 1% aq. sol. gives w. FeCl, an OYS! 
color, changing within 15 min. to OYS2.—V. dil. FeCl; gives 
bluish color.—Reduces AgNO; sol. in the cold.—Apply 


Diethyl Hydroquinonedicarbonate, CsH,O;.Et:.—Sbl. in flat 
greenish lft. w. bluish fluorescence.—D. s. ¢. alc.; sol. fluo- 
resces blue in reflected light, pale greenish yellow by trans- 
mitted light.—S. in dil. NaOH w. deep-yellow color.—With 


p-Benzoylphenyl, C,;H,,»0..—Dist.—Lft. d.s. c.aq., more s. h. aq.; 
e. s. alc., eth., and Ac.; s. in alkalies, but reppt’d by acids.— 
Dec. by conc. H4SO; at 200°, giving phenol and benzoic acid. 


1, 6-Dioxynaphthalene, C;o>H;.(OH)2.—D. s. ¢. alc.; e. s. eth.— 


} Furoin, C,H,0.CO.CH(OH).C,H,0.—Nearly colorless (about 
YT3) eryst., d.c. alc.; 47 aq.—Sol. in ¢) cone] Haat) ae 
deep blue-green!—FeCl, gives no coloration.—E. s. ec. 
NaOH to deep bluish-green sol., very deep violet-red by 
transmitted light; color discharged on dilution, after first 
changing to green! ‘The violet-red sol. diluted as much 
as practicable shows heavy absorption bands between 
D and C in orange, and between D and D4}E!—The m. p. 


96 GENUS IV, DIV. A. 
(ORDER I, SUBORDER I.) 
Melee Ue Ve reas PHENOLIC COMPOUNDS.—Colorless and Solid. 
122 
w. h. dil. ammon. AgNO, sol., evolving aldehyde. 
122 285-6 
by Test 413! 
124 2, 5-Dioxytoluene(1), Me.C,H,.(OH),. 
aq., alc., or eth.; less s. bz.; s. alkalies. 
gives brownish-red color. 
aq.) w. m. p. 82°-85°. 
125 276-9 m-Xylorcin, C,H,.(Me,)(OH),(1, 3, 4, 6).—Tbl. e. s. aq. or eth. 
125 
HNO, gives picric and oxalic acids. 
126-7 
—The alc. sol. shows intense light-blue fluorescence. 
128 Ethylsuccinylosuccinic Ac., C,H,O;. 
2H,0O, or 4H,0, pale rose-colored crystals. 
129 
gives same bluish color as pyrogallol. 
129-5 9, 10-Dihydroanthrol(2), C,H,:(CH,),:C,H,OH.—E. s. alc. w. 
blue fluorescence. 
129-31 | 
| violet, and whose Ag salt is dark red! 
133 | 293 (sl. d.) 
1395955 Test 417! 
134 a trace of FeCl; gives a blue-green color. 
134-5 
FeCl; gives a transient blue color, then a copper-red ppr. 
135 
of oxime is 160°-1°; of the phenylhydrazone 79°-80°. 
135-6 


1, 4-Dimethylnaphthol(2), Me,.C,,H,.0OH.—Sbl. fr. 100°.—D, 
s.aq.; s.alc.; e. s. eth.—Zn dust ignition gives dimethyl- 
naphthalene.—Acetate, m. p. 77°-78°. 


i a ee. So 


Meiting-point Boiling-point 
yk (C29. 


135-6 
139 


139-5 


140 


abt. 140 


140-5 


141-2 
142 


143 


144 


145 


144-6 


GENUS IV, DIV. A. 97 
(ORDER I, SUBORDER I.) 


PHENOLIC COMPOUNDS.—Colorless and Solid. 


o-Oxystilbene, HO.C,H,.CH:CH.Ph.—Alm. i. h. aq.; d. s. ¢ 
alc eee alc 


Butenylonphenol(2), C,,H,,0,—Ndl. d. s. aq.; e. s. ale— 
Aq. sol. deep blue-violet w. FeCl,.—M. p. of oxime 84°-5°, 

Oxythymol, Me.C,H,.(Me,.CH)(OH),(1, 4,2,5).—B. p. 290°. 
—Sbl. undecomposed.—V. dase. 80,7 Ss, Wad) 6. 8. alc: 
or eth.—Oxid. gives thymoquinone.—Occurs in oil fr. 
root of Arnica Montana. 


1,8-Dioxynaphthalene, C,,H,.(OH),.—D. s. h. aq.;_e. s. eth. 
or bz..—Dust provokes sneezing.—Aq. sol. w. FeCl, gives 
flocculent white ppt. which soon becomes dark green.— 
Kasily oxidized.—Diacetate, silvery lfts. fr. ale. (m. p. 
147°-8°). 

| Hematoxylin.—Sol. in alkalies intense purple-red.—Cf. 
Suborder II, A, 1, p. 207. 


Oxyhydroquinone, C, H, .(OH),(1, 2, 4).—V. s. aq., alc., or eth.; 
alm. i. CHCl, CS eh risye aye Ac. sol, exposed to air soon 
browns. —Aq. "sol. w. v. dil. FeCl, gives transient green 
which changes w. Na,CO,, first to dark blue and then to 
wine-red.—A conc. aq. sol. gives dark floc. ppt. w. FeCl. 
—M. p. of triacetate 96-5°. 


Protocotoin, C,,H,,O,.—Pr. fr. ale.—Gives blue-green color 
w. c. conc. HNQO,. *_Dibrom-deriv. fr. Br in CS, sol., scales, 
m. p. 170°. 

Resacetophenone, Me.CO.C,H;.(OH),.(1, 2, 4).—Cryst. d. s. aq. 
—Aq. sol. colored wine-red by FeCl,.M. p. of oxime, 
198°-200° d. 

Dioxyphenanthrene, C,,H,.(OH),.—E. s. NaOH w. green color, 
quickly changing to red.—S. in conc. H,SO,+ trace of 
HNO, w. red color.—V. e. oxidized.—Diacetate, m. p. 
159°. 

Benzoresorcin, Ph.CO.O,H;.(OH),.—Ndl. fr. h. aq.; d.s. c. 
aq.; e. s. ale. or eth.—Alc. sol. becomes brown-red w. FeCl. 
—M. p. of dibenzoate 141°. 


Benzopyrocatechin, Ph.CO.C,H,.(0H),.—V. d. s. c. aq.—Ale. 
sol. w. FeCl, gives rich green coloration, changing to 
red on addition of a drop of ammonium carbonate.—Re- 
duces Tollen’s reagent (cf. Test 101). 


Arbutin, C,;H,,0,, (?) (substance dried in vacuo at 100°).— 
(Statements concerning symbol and m. p. are conflicting; 
m. p. 165° and 170° are also recorded.)—Taste bitter.— 
Lustrous nd) e. s. h. aq. or alc.; i. eth.; more s. in dil. 
NaOH than in aq.—A 1% aq. sol. gives a transient VB-BV 
color w. FeCl,.—Boiled w. x’s of FeCl, sol. gives pungent 
odor of quinone !—(A glucoside hydrolyzed by dil. H,SO, 
to dextrose and hydroquinone.) 
Orcacetophenone, (Me)(OH),.C,H,.CO.Me.—Silky ndl. v. s. alc. 
or eth.; e. s. NaOH or NH,OH.—Aq. sol. black w. FeCl. 
Dioxyayiene Cad: .(Me,)(OH),(1, 3, 2,4).—Sbl. in ndl.; v. s. 
aq., alc., or eth.-—Gives intense violet color w. FeCl,. 

sects P s-Trimethylphendiol, Me,.C,H.(OH),.. — B. p. 275° c.— 
Sbl. in lft.—D. s. c. aq.; e. s. alc. or eth.—Aq. sol. gives 
transient green color and gray ppt. w. FeCl,—Reduces 
ammon. AgNO, sol. 

sah aged ome ete sy (Ce H,.0H),.C.Me,.—I. c. aq.; 

. h. aq.; e. s; alc. or eth. 

Dee Succinylosuccinate, C ,H,O,.Me,.—FeCl, gives red 

color w. ale. sol.—The free acid is unstable. 





98 


GENUS IV, DIV. A. 
(ORDER I, SUBORDER I.) 


rn 


Melting-point 
COR: 


154 
156 
156 


158 


158 


159 


159 


160 


161 


161 
161 
161 


162-3 


163 


Boiling-point 
(Ce). 


PHENOLIC COMPOUNDS.—Colorless and Solid. 


Bicarvacrol, C,,H,,0,.—Silky ndl.; i. aq.; e. s. alc., eth., or bz. 


I, 2, 4-Trimethylphendiol(3, 5), Me,.C,H.(OH),. 


Anemonin, C,,H,O,—Vol. w. st.—Lustrous ndl. fr. alc., or 
plates fr. CHCI, -—D.s. h. aq. ore. ale.; 1. eth—-Ale "sol. 
reacts neutral. ap s. alkalies w. yellow-red to blood-red . 
color.—A few degrees above m. p. solidifies to yellow com- 
pound which decomposes at 290°.—Combines w. phenyl- 
hydrazine. 


p-Dioxydiphenylmethane, CH,.(C,H,OH),.—Sbl.—Not vol. w. 
st.—E. s. alc.; v. s. eth.; s. CHCl,; i. CS,; s. in NaOH 
and ppt’d by CO,.—Aq. sol. colored brown-yellow by 
FeCl,.—Aq. sol. of disodium salt is green.—Fusion w. 
KOH gives p-oxybenzoic ac. and phenol (Test 414). 


+ Convolvulin, C,.H,,0,, (?).—Amorphous.—Alm. i. aq. or eth.; 
e.s. alc.—Mix a few mgr. w. adrop of c. conc. H,SO, After 
5 min. a VR color appears, changing after 4 hr. to R.— 
Warm a little w. x’s of conc. H,SO,; disagreeable odor of 
rancid butter, changing to sharp odor if temp. is increased. 
—S. NaOH w. dec.—A glucoside fr. jalap root (Convol- 
vulus purga), aoa dextrose, etc., on hydrolysis by h. 
baryta water. 


Maltol, C,H,O.(OH),.—Sbl. in Ift.—D. s. bz. or ec. aq.; v. s. 
CHCl, or h. aq.; s. NaOH, but reppt’d by CO,.—Aq. sol. 
colored an intense violet by FeCl,—Reduces ammon., 
Ag sol. c., or Fehling’s sol. when hot. 


2, 3- TiGeeie ont C, ,H,.(OH),.—Rhombic lft. fr. aq.— 
S. h. aq.; e. s. ale. or eth.—Gives intense dark-blue BAS. 
w. FeCl. 


} Zsculin, C,,H,,0,.—White lustrous odorless ndl, slightly 
bitter taste.—Loses cryst. aq. at 120°-130°.—S. in 600 pt. 
c., or 12-5 pt. h. aq.; d.s. c. alc. or eth.; e.s NaOH — 
The cold supersaturated aq. sol. gives blue-green color 
(BG) w. FeCl,.—V. dil. aq. sol., especially in presence of 
a trace of alkali, shows a magnificent light-blue (BT2) fluo- 
rescence! Shaken w. little HNO, gives yellow sol., which 
becomes deep blood-red upon addition of NH,OH!— 
Hydrolysis by h. dil. HCl gives dextrose and eesculetin — 
Gives the Molisch color reaction in Test II w. e-naphthol. — 
(In bark of the horse-chestnut ) 


4; 4-Dioxytriphenylmethane, Ph.CH.(C,H,OH),.—Ndl. fr dil. 
alc.; 1. c., d. s. h. aq.; e s alc. or eth—Diacetate melts 
at 109°- 111°, 

o-Bicresol, (Me.C,H;.0H),.—D. s. h. aq.; e. s. ale. or eth— 
Diacetate m. p. 131°. 

Benzyhydroxylphenol, Ph.CHOH.C,H,.OH.—D. s.c aq.;e. 8, 
alc. or eth.; s. alkalies —Aq. sol. colored red by FeCl. 


d-Biphenol, (C,H, .OH),—B. p 342° Ndl, v. ds h. aq.; 
v. s. ale. or eth. —Aq. sol. gives ppt w. PbAc, —Diacetate 
melts at 94°. 


3, 3’-Dioxybenzophenone, (C,H,OH),-CO.—E s. KOH but re- 
precipitated by CO,.—Fusion w. KOH gives phenol and 
oxybenzoic ac. 


B-Orcin, C,H,.(Me,)(OH),(1, 4, 3,5).—B. p. 277°-80° —Much 
less s. aq. than orcin —NH, H sol w. Ca(OCl), gives clear 
carmine-red color.—Boiled w. Mail NaOH and CHCl, gives 
deep-red sol. w. green fluorescence like orcin !—Tetra- 
brom-derivative, ppt’d by Br aq., cryst. fr. lgr. w. m. p. 
101°.—Phthalic ‘anhyd. fusion Rives no color, 





160-70d. 


165-5 


168 
168 


168-70 


169 


169 


abt. 170 


171 
173-4 


175 
176 
178 
180 


184 


184-5 





GENUS IV, DIV. A. 99 


(ORDER I, SUBORDER I.) 


oe ae are hale ll Meet ae ae TS i ee ee 
Melting-point 
CC}; 


PHENOLIC COMPOUNDS.—Colorless and Solid. 


{ Anthranol, C,H,:C,H(OH):C,H,.—Lustrous v. pale-yellow 
(about YT3) ndl—kE. s. h. bz. Does not dissolve fully 
in c. alkali, but becomes bright yellow and gives a yellow 
filtrate; reppt’d by CO,.—The alkaline sol. when boiled 
in presence of air absorbs O, giving much anthraquinone! 
—Dissolve a small quantity in cold fuming HNO,; dilute 
w. aq. and dissolve orange ppt. in alc. containing 1 drop 
NaOH sol.; an intense violet-red color is produced!— 
Ignition w. Zn dust gives anthracene (Test 912). 

Bithymol, C,,H,,0,+H,O.—I. aq.; e. s. alc., eth., or bz.; s. in 
alkalies w. orange color. 

Arbutin, cf. IV, A, m. p. 144°-6°. 

Trioxyacetophenone (Gallacetophenone), (HO),.C,H,.CO.Me.— 
Pearly lft., e. s. h. aq—S. m NaOH w. brownish color; in 
conc. H,SO, w. clear yellow color.—Picrate, yellow ndl., w. 
m. p. 133°.—Oxime, ndl. fr. toluene w. m. p. 162°-3°. 

a-Hydrojuglon, C,,H,.(OH),(1, 4,5) (fr. the walnut-tree, Ju- 
glans regia).—Cryst., s.in 200 pt. aq. at 25°; v. s. alc. or eth.; 
i. CHCl, or bz.; e. s. alkalies w. intense yellow color which 
changes in air to red.—Br or FeCl, gives juglon. 

+ Hydroquinone, p-C,H,.(OH),.—Sbl. in Ift.—Taste slightly 
sweetish.—S. in 17 pts. aq. at 15°; e. s. ale. or eth.—The 
cold saturated aq. sol. gives a YO colored sol. w. FeCl, in 
Test 401.—Boiled w. excess FeCl, gives pungent odor of 
quinone.—Alkaline sol. browns in air.—Reduces AgNO, on 
warming, and Fehling’s sol. in the cold.—Identify by 
Test 411! 

I, 2, 4-Trimethylphendiol(3, 6), Me,.C,H.(OH),.—-D. s. c. aq.; e. 
s. h. aq., alc., eth., or bz. Diacetate, m. p. 112°. 

Phloridzin, C,,H,,0,,.—Taste bitter!—Silky ndl. wh. first melt 
at 108°-9°, losing 2H,O of cryst., and then solidifying at 130°. 
—S. in 1000 pt. c. aq.; e. s. h. aq. or alc.; alm. i. eth.; sol. 
in NaOH absorbs O, becoming red-brown.—Sol. dark violet 
w. FeCl,.—A glucoside readily hydrolyzed by boiling w. dil. 
H,SO, to phloretin and dextrose. 

Tetraoxytriphenylmethane, Ph.CH.[C,H,.(OH),],.—D. s. aq.; e. 
s. alc. or eth.—Kasily oxid. to resorcinbenzein. | 

2-Acetylnaphthol(4), Me.CO.C,,H,.OH.—Ndl. e. s. alc_—FeCl, 
gives floc. ppt. w. aq. sol.—Ppt’d fr. sol. in alkali by CO,.— 
KMn0O, oxid to phthalic ac. (Test 318). 

1, 4-Hydronaphthoquinone, C,H,.(OH),.—Long ndl. s. h. aq.; 
e. s. h. alc. or eth.; alm. i. CS,.—CrO, oxid. to a-naphtho- 
quinone.—Diacetate melts at 128°-30°. 

Phenyl p-Oxybenzoate, HO.C,H,.CO,Ph.—Saponification by 
Test V very easily gives p-oxybenzoic ac. and phenol (Test 
414). 

1, '7-Dioxynaphthalene, C,,H,.(OH),.—S. aq.; e. s. alc. or eth.— 
Aq. sol. gives deep-blue ppt. w. FeCl,;.—Alkaline sol. blackens 
in the air.—Diacetate melts at 108°. 

Benzoylsalicin (Populin), C,,H,.0,.—Cryst. w. 2H,O (lost at 
100°).—Taste sweetish.—S. in abt. 2000 pt. c. aq.; s. cone. 
KOH.—Conc. H,SO, colors amethyst-red.—Saponified by 
h. Ba(OH), to salicin and benzoic ac. (Test 412). 

I, 3, 5-Trimethylphloroglucin, Me,.C,.(OH),.—S. alkali carbon- 
ates.—Br gives derivative w. m. p. 90°. 

Filixic Ac., C,,H,,0, (fr. Aspidium Filix mas.).—Mic. lft. fr. 
eth.—lI. aq.; alm. i. alc.; s. eth—Reduces ammon. AgNO. 
—Fusion w. KOH gives phloroglucin (cf. Test 415). 





100 





Melting-point 
(C.°). 


185 


185 


186 


186 


190 


190 


190 


194d. 


198-200 


200 
200 


200d. 


200 or 210d. 
200-5 


201 


202-3 


200-9 (s. h.) 


GENUS IV, DIV. A. 


(ORDER I, SUBORDER I.) 
eR 


PHENOLIC COMPOUNDS.—Colorless and Solid. 





Dithymolethane, Me.CH.(C,,H,,OH),.—Dist. undecomposed.— 
Ndl. fr. bz., plates fr. ale—Oxid. by MnO, and dil. H,SO, 
gives thymoquinone (Suborder 2, m. p. 45-5°). 


} Coniferine, C,, H,.0,+2H,0.—I. c. aq.; v.s. h. aq. or dil. alka- 
lies—Warmed with conc. HCl turns cobalt-blue.-—Warmed 
w. conc. H,SO, gives violet sol. changing to violet-red.— 
Gives no ppt. w. PbAc,.—Gives no color w. FeCl. 


Iretol, C,H,.(MeO)(OH),(2, 1, 3,5).—Ndl. e. s. aq., alc., or eth. 
—Br aq. gives hexabromacetone.—HNO, oxid. to oxalic ac. 
(Test 317). 


Irigenin, C,,H,,0,.—Rhombohedra fr. dil. alc.; d.s. aq.; i. eth. 
or lgr.—Aq. sol. deep violet w. FeCl,. 


Phenolphthalol, (HO.C,H,),.CH.C,H,.CH,OH.—Pr. d. s. h. aq.; 
e. s. alc. or eth.; 1. bz. or CHCl,.—Becomes red w. conc. 
H,SO,.—Alkaline potassium ferricyanide oxid. to deep-red 
solution of phenolphthalein. 


2, 7-Dioxynaphthalene, C,,H,(OH),.—Nadl., sbl. w. dec.—E. s. 
h. aq., alc., or eth.; alm. i. CS,.—Transient dark-red color 
w. Ca(OCl),.—Alkaline sol. darkened by air.—M. p. of 
diacetate 129°-30°. 


Hydroceerulignon, (MeO),.C,,.0,.(0H),.—Monoclinic pr. fr. ale.— 
V.d.s. aq. or eth.; s. h. ale. or bz.—Reduces c. ammon. Ag 
sol.—F eCl, on exposure to air causes separation of coeru- 
lignon. 


Methylene-di-@-Naphthol, CH,.(C,,H,OH),.—Mic. ndl., e. s. alc.; 
alm. i. CS,.—M. p. of diacetate 211° (i. alc.; e. s. bz.).— 
Picrate melts at 178°-9°. 


Diethyl-p-diphenol-methane, Et,.C.(C,H,.OH),.—Pr. fr. alc.; i. 
h. aq.; e. s. alc. or eth. 


Resorcinphthalein.— Yellowish crystals.—Cf. Suborder 2, 


} Picrotoxin, C,H;,0,, (from Menispermum  Cocculus).— 
Cryst. s. 300-400 pt. c. aq.; e. s. alc. or h. aq.; e. s. in NaOH, 
the sol. soon becoming golden yellow.—The color of a sol. 
obtained by dissolving afew crystals in conc. H,SO, on eruci- 
ble cover is a strong orange-yellow (OY) !—Taste of aq. sol. 
(1:10,000) intensely bitter !—No pronounced color w. FeCl. 
—Gives ppt. w. Br aq.—Reduces AgNO, sol. when warmed. 
(Very poisonous.) 

Daphnin, C,,H,,0,.—(Loses 2H,O of cryst. at 100°.)—Colorless 
pr. w. bitter astringent taste !—D. s. c. aq.; e. s. h. aq. or h. 
alc.; i. eth.; s. NaOH or Na,CO, w. yellow color.—FeCl, 
colors the solution bluish.—HNO, gives red color in the cold, 
—Hydrolyzed by dil. acids to dextrose and daphnetin. (In 
bark of Daphne Mezereum.) 

Tannic Ac., C,,H, ,0,.—See ITI, A, 1, m. p. 210°. Taste astringent, 

Phenoglucin, C,H,O,+ 2H,O.—Taste very sweet.—Pr. fr. aq.— 
Gives pale-violet color w. FeCl,. 

ft Salicin, C,,H,,O,—Taste bitter—A glucoside.—Hydrolyzed 
by h. dil. H,SO, gives dextrose and saliretin; by emulsin 
gives dextrose and saligenin.—Cryst. s. 28 pt. aq. (15°); 
more s. in NaOH; i. eth.—Gives no color w. FeCl,.—The 
powder stirred into conc. H,SO, on crucible cover gives 
bright scarlet (OR) color! . 

Hydroquinonphthalin, C,.H,,0;—Oxid. agents give hydro- 
quinonphthalein. 

Phloroglucin.—See m. p. 217°-19°. 








GENUS IV, DIV. A. 101 


(ORDER I, SUBORDER I.) 











Be |) Pome point PHENOLIC COMPOUNDS.—Colorless and Solid. 
206 4-4’-p-(or a)-Dioxybenzophenone, CO.(C,H,OH)..—Dist. unde- 


composed.—Cryst. fr. h. aq., e. s. alc., eth., or alkalies — 
Ppt’d fr. Ba(OH), sol. by CO,.—No color w. FeCl, .—F usion 
w. KOH gives CO, and phenol. —Tetrabrom substitution 
product fr. alc. sol. of compound w. Ac sol. of Br in cold, 


m. p. 213°-14°. 
206-8d. Anhydrobisdiketohydrindene, C, .H,,0;.—Sol. in alkalies intense 
red to violet; ppt’d by CO,.—Oxime d. at 210° without 
melting. 
212 Phenolphthalidein, C,,H,,0,—S. alc. or eth.; s. alk. w. pale 
yellow and in conc. H,SO, w. intense violet ‘color. 
212 Hydrophloron, C,H,.(Me,)(OH),(1, 4, 2, 5).—Sbl. in Ift., s. h. aq.; 


v. 8. alc, or eth.; d.s. CS, —Boiled w. FeCl, or dil. HNO, 
gives phloron. —Reduces Ag sol, 

212-13 Acetonresorcin, Me.CO.(C,H,OH),+ H,O.—I. aq., CHCl, bz., or 
abs. eth.; s. NaOH.—Resorcin and acetone are among the 
products of decomposition by heat. 

210-20 a-Tribenzoylmethane, (Ph.CO),.C:(HO)C.(Ph).—S. in CHCl, or 
aq.—Freshly prepared gives pale-yellow sol. in 1% Na,CO,, 
and a deep-red color w. FeCl,. After fusion or keeping goes 
over to neutral 8-modification, WwW. m. p. 225°-6°. 

215-16 2, 6-Dioxynaphthalene, C,,H,.(OH),.—-Sbl. in pearly lft.—D. s. 
c. aq.; e. s. ale. or eth.—Aq. sol. gives yellowish-white color 
w. FeCl, .—M. p. of diacetate 175°. 

215-20 I, 2, 4, 5-Letroxybenzene, C,H,.(OH),.—Silvery lft. fr. Ac.—E. 
s. aq., eth., or alc. —Quickly oxid. by FeCl, or by air in alka- 

line sol. to dioxy quinone. 

217-19 (r. h.) { Phloroglucin, C,H,.(OH),.(1, 3,5).—Loses 2H,O cryst. on 

heating to 100°. “Spl. w. sl. decomposition. —Taste sweet- 
ish.—E. s. aq., alc., or eth.—A 1% aq. sol. in Test 401 w. 
FeCl, gives BV-V coloration, which fades rapidly.—Sol. in 
NaOH absorbs O, but less rapidly than pyrogallol.—A pine 
splinter first well soaked w. conc. HCl assumes a deep-red 
coloration (R-VR) when dipped in a dilute aqueous sol. of 
phloroglucin !—The aq. sol. gives a heavy ppt. of tribrom- 
phloroglucin, which when purified melts at 151°.—Identify 
by Test 415! 

218c. G-Binaphthol, (HO.C, ,H,),.—Distillation gives 6-naphthol (Test 
413).—Flat ndl. fr, alc.; i. aq.; s. alc.; e. s. eth. Gives 
greenish color w. FeCl, becoming bright red on heating.— 
Picrate, e. s. alc., has m. p. 174°. 

218-19d. Fustin, C,.H,,0.3 (?). SrWhite lustrous ndl., e. s. h. aq. or ce. dil. 
NaOH; d. s. eth.—FeCl, gives green coloration changed to 
blue-violet and red by Na,CO, !—PbAc, gives yellow ppt.— 
(A glucoside; hydrolyzed by dil. H,SO, giving fisetin and a 
carbohydrate.) 


220d. Methylenedipyrocatechin, CH,.[C,H,.(OH),],.—D. s. alc. or eth. 

222 Di-p-Oxyhydrobenzoin, C,,H,,0,.—Cryst., e. s. h. aq. ; less s. alc. ; 
1. eth.—(Forms a Na salt.) 

223-4 Umbelliferon, C,H,O,.—I. c. aq.; s. ale. and h. aq.—S. w. in- 


tense blue fluorescence i in cone. H,SO,.—When warmed has 
odor like coumarin.—s. in cold KOH, but on heating the 
sol. to 60° gives umbelliferic ac. 


224 4-Oxyxanthone, C,,;H,O,.—Sbl. easily—White ndl. fr. ale.— 
Acetyl derivative, mic. cryst. fr. dil. ale., m. p. 137°-8°. 
223-6 (r. h.) 6-Tribenzoylmethane, (C,H,.CO),CH. Pall DOL Ce aC. 
CHOI, or bz.3 1, NaOH. 
226-7 Hydroquinonephthalein, C,H, ,0;.(0H),.—Ndl. fr. eth—S. in 


alkalies w. deep-violet color. 


rere 


102 


GENUS IV, DIV. A. 


(ORDER I, SUBORDER I.) 





Melting point Boiling-point 
(Coy (C2): 


222—40d. 


d. 230 
231 


235d. 


257 Sl... 


241d. 
242 
d. w. m. 245 
248 


abt. 250 


250 


d. w. m. 250 


251d. 


250-3 


252d. 


252-4 


PHENOLIC COMPOUNDS.—Colorless and Solid. 





{ Gallic Ac., (HO),.C,H,.CO,H(3, 4, 5, 1).—Cryst. w. 1H,O (lost 
at 120°) in silky ndl.; s. 130 pts. aq. at 12-5°.—Aq. sol. 
absorbs O from air and turns brown during titration; gives 
no ppt. w. sol. of gelatine (dif. fr. tannic ac.). 


Orcinphthalein, C,,H,,0;.(0H),.—Pr. i. aq.; e. s. ale. oreth. S. 
in alkalies w. intense dark-red color without fluorescence. 


2-Oxyxanthone, C,,H,O,.—Lustrous yellowish ndl. fr. ale.— 
Acetyl derivative, ndl. fr. dil. ale., m. p. 161°. 


G-Quinovin, C,,H,.0,, (?).—(A glucoside of quinovic ace. 
and quinovase-ethylether found in Cuprea bark.)—Cryst. 
seales fr. dil. ale.; alm. i. aq. or abs. eth.; s. alkalies.—Sol. 
in conc. H,SO, is yellow, becoming cherry-red on exposure 
to air. 


Bihydroquinone, [C,H,.(OH).],.—Taste very sweet.—Lft. e. s. 
aq.; v.s. alc. or eth.—Aq. s. w. little FeCl, gives red color; 
x’s of reagent gives biquinone. 


Methylenedipyrogallol, CH,.[C,H,(OH),],.—Cryst. powd. 

3, (3)-Oxyxanthone, C,,H,O,.—Colorless ndl., e. s. NaOH sol.— 
FeCl, added to ale. sol. gives brown color. 

Diresorcinphthalein, C,,.H,,0O,+34H,0.—Silvery lft. fr. aq.—S. 
in alkalies w. indigo-blue color. 

Tetraoxytetraphenyl-ethane, C,,H,,.(OH),.—Scales i. aq.; e. 8. 
alc. or eth. 

{ Brazilin, C,,H,,0;—Cryst. in colorless ndl. w. 14H,O, soon 
assuming a broken orange-red color on exposure.—Taste at 
first faintly bitter, then very sweet /—Sol. in NaOH intense 
carmine-red (R); in cone. H,SO, YO.—f Boil gently in a 
test-tube resting on a perforated asbestos screen, as de- 
scribed in Test 311-2, for 15 min., 0-1 grm. brazilin, 0-15 
erm.fused sodium acetate, and 2-0 cc. acetic anhydride. 
Cool. Add 10 cc. water to residue, and boil. Cool. 
Filter. Dissolve cryst. in 10 cc. boiling dil. ale. (1:1). 
Cool. Filter. Repeat eryst. and filtration twice more as 
above directed. Dry crystals at 100° and determine melting- 
point.— The product, tetraacetylbrazilin, melts at 149° 
(uncor). . 

1, 5-Dioxynaphthalene, C,,H,.(OH),.—D. s. aq.; e. s. eth.—Re- 
duces Fehling’s or ammon. Ag sol.—CrO, oxid. to the quin- 
one.—Diacetyl compound has m. p. 159°-60°. 


Methylenediresorcin, CH,.[C,H;.(OH),.],.—The alkaline sol. ab- 
sorbs O from the air and reddens. 


Hesperidin, C,.H,,0,, (?).—Odorless, tasteless cryst. powder, s. 
5000 pt. =. aq.; 1. eth.; d.s. ale.; s. NaOH but reppt’d by 
CO,.—The sol in NaOH on evaporating to dryness and treat- 
ing w. x’s H,SO, and warming gives red to violet color !— 
[A glucoside hydrolyzed by boiling w. dil. acids to glucose 
and hesperitin (latter melts at 224°-6°, and is s. in alkalies 
and cclored brown-red by FeCl,).] 

{ Phenolphthalein, C,,H,,0,.— When amorphous e. s. eth.; when 
cryst. d. s. eth.; s. alc.; i. aq.—S. in NaOH or Na,CO, w. 
intense red color, approximately RV, but much purer than 
color of the standard. The color is discharged by large x’s 
of NaOH or by warming w. Zn dust. 

Tetraoxydinaphthylmethane, CH,.[C,,H;.(OH),],.—E. s. ale. or 
eth.—S. in conc. H,SO, w. yellow color, changing to deep red. 

Thymolphthalein, C,,.H,,O,.—_Ndl., e. s. ale.; s. eth.; alm. i. aq. 

NaOH gives intense blue sol. (purple by transmitted light), 








a a ae 


Melting-point Boiling-point 
CO.2): (C2). 


Se 


253-5d. 


253-6 


a, 270d. 


272 


d. w. m. 275 


280d. 


300 


310 


GENUS IV, DIV. A. 103 


(ORDER 1, SUBORDER I.) 





PHENOLIC COMPOUNDS.—Colorless and Solid. 


Phloretin, C,,H,,0,.—Lft. v.d.s. h. aq. or eth.; v.s.alce.—Sol. in 


alkalies absorbs O fr. air.—Boiled w. KOH gives phloretic 
ac. and phloroglucin.—Heated w. aniline at 170° gives scarlet 
sol.—Anilide, alm. i. aq. or eth., but s. in alc. w. deep-orange 
color. 


+ Daphnetin, C,H,0,.(OH),.—Yellowish ndl. w. coumarin-like 
odor when warmed!—Sbl.—S8. h. aq.; v. d. s. eth.; s. 
Na,CO, w. orange color.—Aq. sol. gives green color w. 
FeCl;, becoming red w. Na,CO;.—Gives yellow ppt. w. 
PbAc,.—Diacetyl deriv., m. p. 129°-30°. 

| Zisculetin, C,H,O,.(OH),+H,0.—(After loss of cryst. aq. be- 
comes yellow.)—Lustrous ndl. v. d. s. c. aq.; s. h. aq.; alm. 
i. eth.; s. in NaOH w. yellow color.—FeCl, gives intense 
green color w. aq. sol. !—PbAc, gives yellow ppt. fr. sol.! 

r-(p)-Biphenol, [C,H,.OH],.—Sbl. in scales.—D. s. aq.; e. s. ale. 
or eth.—Aq. sol. gives no color w. FeCl, and very transient 
violet w. Ca(OCl),.—Sol. in H,SO, and trace of HNO, be- 
comes blue.—Ignition w. Zn dust gives biphenyl.—Diacetate, 
m. p. 159°-160°. 

Arabinose-resorcin, C,,H,,0,.—Amorph. powder, v. s. aq.; Vv. 
d. s. alc. or eth.—Aq. sol. blue-violet w. FeCl,; intense red- 
violet w. Fehling’s sol. 

p-Dioxystilbene, (HO.C,H,.CH:),.—E. s. eth.—Diacetate, d. s. 
h. ale.; m. p. 213°. 

a-Binaphthol, [C,,H,.OH],.—Sbl.—I. aq.; s. ale.; more s. eth._— 
Alec. sol. gives violet-red color w. FeCl, and ppt. of same 
color. 

Biresorcin, C,,H, 0,-+2H,0.—Cryst. s. h. aq.—FeCl, gives pale- 
blue color.—Heated at 100° for 10 min. w. 1 cc. H,SO,+1 ce. 


acetic anhyd. gives blue-violet sol.—M. p. of tetraacetate 
158°. 





COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER J] 


GENUS IV, PHENOLIC COMPOUNDS. 


DIVISION B,—LIQUID PHENOLIC COMPOUNDS. 


Boiling-point 
(Ce). 


139-6 


158 


167-70 


169 
169-70c. 


174-5 


180-5 


183 
186-8 


189-7c. 


191 
196 


198e. 


201 


201-8 
202-8 


Specific 
Gravity. 


0-987 (15°) 


0-954 (15°) 


0-994 (4°) 
1-037 (9°) 


0-941 (15°) 


1-046°/, 


1-009 (6°) 


0-995 (14°) 


0-998 (12°) 


0-981 (0°) 


1-050 (0°) 





PHENOLIC COMPOUNDS.—Colorless and Liquid. 


+ Acetylacetone, Me.CO.CH,.CO.Me.—Odor like acetone and 


acetic acid.—S. in 8 pt. aq.—The color of aq. sol. (1:100) 
w. FeCl, (Test 401) is a very permanent OR-RO.—Dis- 
tinctly acid!—The aq. sol. gives heavy light-blue ppt. w. 
sol. of CuAc,.—Saponification by Test V gives acetone and 
acetic ac. (Tests 711 and 311). 

Hexanedione(2, 4), Me.CO.CH,.CO.Et.—Has acid properties.— 
Cu salt obtained by ppt’n of sol. in dil. ale. w. CuAc, sol., 
blue ndl. fr. alc., m. p. 197°-8°. . 

3-Methylhexanedione(2, 4), Me.CO.CHMe.CO.Et.—Blue ppt. w. 
ammon. CuCl sol., m. p. 192° 

3-Methylpentanedione(2, 4), Me.CO.CHMe.CO.Me. 

Methyl Acetoacetate, Me.CO.CH,.CO,Me.—E. s. aq!—Sol. dark 
cherry-red w. FeCl,!—Saponification by Test V-2 gives 
acetone and CH,OH. 

2, 4-Heptanedione, Me.CO.CH,.CO.Pr.—Gives a Cu salt, m. p. 
160°-1°. 

+ Ethyl Acetoacetate, Me.CO.CH,.CO,Et.—An aq. sol. (1:100) 
gives a clear and very permanent RT1 color w. FeCl, (Test 
401).—Saponification by Test V—2 gives acetone, C,H,OH 
and CO, (cf. Tests 711 and 814). 

+ Phenol (cf. IV, A, m. p. 42-5°). 

Ethyl Methylacetoacetate, Me.CO.CHMe.CO,Et.—Sol. colored 
blue by FeCl,.—Saponification by Test V gives methyl ethyl 
ketone, C,H,OH and CQ,. 

Methyl Ethylacetoacetate, Me.CO.CHEt.CO,Me. — Violet-red 
color w. FeCl,.—Saponification by Test V gives methyl 
propyl ketone and CQ). 

o-Cresol (cf. Genus IV, A, m. p. 30°). 


Caffeol, HO.C,H,.CH,.0.Me.—Odor like coffee-—D. s. h. aq.; 
e s. alc. or eth.—Aq. sol. colored red by FeCl,.—Fusion w. 
KOH gives salicylic ac. (Test 319). 

Ethyl Ethylacetoacetate, Me.CO.CHEt.CO,Et.—Sol. colored blue 
by FeCl,—Saponification by Test V gives methyl propyl 
ketone, C,H,OH, and CO,. 

Ethyl Isopropylacetoacetate, Me.CO.CHPr.CO,Et.—Sol. colored 
pale red-violet by FeCl;.—Saponification by Test V gives 
methyl isobutyl ketone, C,H,OH, and CO,. 

+ p-Cresol (cf. IV, A, m. p. 36°). 


+ m-Cresol, Me.C,H,.OH.—Does not solidify at 0°.—The color 
w. a 1% aq. sol. and FeCl, (cf: Test 401) is BV-BVT1 (on 
mixing).—Odor like phenol.—Not sol. in 5 pt. conc. ammo- 
nia.—f{ Nitrate and purify the product, 2, 4, 6-trinitrocresol, 
by the procedure given in Test 414-2 for phenol. This tri- 
nitrocresol is a cryst. compound resembling picric acid in 
most of its properties, but melting at 106-5° (uncor.). 





104 


GENUS IV, DIV. B. 105 


(ORDER I, SUBORDER I.) 


ES 


Boiling-point 
(CORSE 


204-6 


205 
205-6 
206 
207c. 
208:°5 


211-5 
213c. 


214 
217°5 


221-2 


224c. 


225c. 
227-5 


231c. 
231 


231-5 


236- 5-7 


238-40d. 


238—40 


240—-41c. 


242 


243 


Specific 
Gravity. 


1-086 (15°) 
0 5 9327°) 


1-037 (0°) 
0-9819/, 
1-012°/, 

1-025 (0°) 

0-951 (17-5°) 


1-111 (0°) 


1-197 (0°) 


1-015 (0°) 


1-009 (0°) 


0-986 (15°) 


1-098 (15°) 
1-098 (15°) 
1-056 (15°) 
1-144 (23°) 


1-140 (23°) 


PHENOLIC COMPOUNDS.—Colorless and Liquid. 





Acetylmesityloxide, Me.CO.CH,.CO.C,H,.—S. in alkalies—Alc, 
sol. is colored intensely red by FeCl;.—Olive-green Cu salt, 
m. p. 123°. 

1 Guiacol (cf. IV, A, m. p. 31°-2°). 

Veratrol, o-C,H,(OMe),.—Solid at +15°. 

Ethyl Allylacetoacetate, Me.CO.CHC,H,.CO,Et.—Sol. colored 
carmine-red by FeCl;.—Saponification by Test V gives allyl- 
acetone, C,H,OH, and COQO,. 

Phlorol, o-Et.C,H,.OH.—Not solid at —18°.—Violet color w. 
little FeCl;.—Fusion w. KOH gives salicylic ac. (Test 319). 

Ethyl Propylacetoacetate, Me.CO.CHPr.CO,Et.—Saponification 
by Test V gives methyl butyl ketone, C,H,OH, and CO,. 

1, 3-Xylenol(1) (cf. IV, A, m. p. 26°). 

o-Isopropylphenol, Me,.CH.C,H,OH.—M. p. 15°.—Aq. sol. violet 
and then green w. FeCl. 

m-Ethylphenol, Et.C,H,OH.—M. p. abt. —4°.—Violet w. FeCl. 

Ethyl Isobutylacetoacetate, Me.CO.CH(C,H,).CO,Et.—Saponifi- 
cation by Test V gives isobutylacetone, C,H,OH, and €Q,. 

Homopyrocatechinmethylether, Kreosol, 
C;H;.(Me)(MeO)(OH)(1, 3, 4).—Mliscible w. alc. or eth.— 
Alc. sol. emerald-green w. FeCl;.—M. p. of picrate 96°. 

t+ Methyl Salicylate, o-HO.C,H,.CO,.Me.—Odor of oil of winter- 
green.—The color of the cold saturated aq. sol. w. FeCl, 
(Test 401) is RV, permanent for more than 15 minutes.— 
Saponification by Test V gives salicylic ac. and CH,OH 
(Tests 319 and 819). 

o-Propylphenol, HO.C,H,.Pr. 


Ethyl Isoamylacetoacetate, Me.CO.CH(C,H,,).CO,Et.—Saponi- 
fication by Test V—2 gives isoamylacetone, C,H ,OH, and CO). 

p-Propylphenol, HO.C,H,.Pr. 

Isocymophenol, C,H,.(Me)(Pr)(OH)(1, 3, 6).—Not solid at —25°. 
—S. aq.—Aq. sol. pale-violet w. FeCl,—Vapor induces 
coughing. 

+ Ethyl Salicylate, o-HO.C,H,.CO,Et.—Odor of oil of wintergreen. 
—The color of the cold saturated aq. sol. w. FeCl, (Test 401) 
is RV (on mixing); VRT2-RVT1 after 15 minutes.—Saponi- 
fication by Test V—2 gives salicylic ac. and C,H,OH (Tests 
319 and 814). 

{ Carvacrol, Me.C,H;.(Pr)(OH)(1, 4,2).— Viscous oil which 
solidifies at —20°.—FeCl, gives a coloration, but only in very 
conc. alc. sol.; the color is then an impure green, which 
changes and fades rapidly.—M. p. of the phenylcarbamate 
140°.—(Cf. Ber. 26, 2086.) 

Diethyl Acetylmalonate, C,H,0.CH.(CO,Et),.—Has a strong ae. 
reaction! Alc. sol. dark red w. FeCl,;—Phenylhydrazine 
derivative melts at 120°.—Saponification by Test V-2 gives 
acetone, acetic ac., and C,H,OH (Tests 711, 311). 

Propyl Salicylate, PrCO,.C,H,.OH.—Saponification by Test V—2 
gives salicylic ac. and C,H,OH (Tests 319 and 820). 

Cerulignol, HO.C,H, ,.OMe.—Odor like creosote.—V. d.s. ¢. ad. : 
miscible w. alc. or eth.—Aq. sol. gives carmine ppt. w. FeCl . 
—aAle. sol. green w. FeCl, and blue w. Ba(QH)),. 

Methyl 4-Oxy-m-toluate, HO.C,H,(Me).CO,Me.—Oil of winter- 
green odor.—Saponification by Test V gives 4-oxy-m-toluic 
ac. and CH,OH (Test 819-1). 

Methyl 3-Oxy-p-toluate, HO.C,H,Me.CO,Me.—Saponification by 
Test V—2 gives 3-oxy-p-toluic ac. and CH,OH (Test 819-1). 





106 


GENUS IV, DIV. B. 


(ORDER I, SUBORDER I.) 





Boiling-point 
COE 


243-4 


247-5sl. d. 


248 


254 


254-5 


254-6 


258-62 


265-70d. 


266-9 
270 
273 


283-4 








Specific 
Gravity. 


1-063 (18-5°) 


1-102 (23°) 


1-097 (23°) 


1-067 (15°) 


1-088 (15°) 


1-080 (16°) 


1-122 (15°) 


1-03615/,, 


PHENOLIC COMPOUNDS.—Colorless and Liquid. 





Methylresorcin Ether, m-HO.C,H,.OMe.—S. c. aq.; miscible w. 
alc. or eth.—Aq. sol. pale violet w. FeCl,. 

+ Eugenol, C,H;.(CH,.CH: CH,)(OH),(1, 3, 4).—Odor of cloves. 
—V.d.s.aq.; e.s. alc., eth., or Ac.—Cold saturated ag. sol. 
gives a turbid YGT2 color in Test 401, w. FeCl,; the alc. sol. 
(1:50) gives a B color fading in 15 min. to GYT2. 

Ethyl 1-Methyl-2-oxybenzoate(3), Me.C,H,(OH).CO,Et.—Sapon 
equiv. 178.—The corresponding ac. gives violet color w. 
FeCl;.—Saponification by Test V—2 gives 1-methyl-2-oxy- 
benzoic ac. and C,H,OH (Test 814). 

Ethyl 3-Oxy-p-toluate, HO.C,H,(Me).CO,Et.—Saponification by 
Test V—2 gives 3-oxy-p-toluic ac. and C,H,OH (Test 814). 

Betelphenol, (CH,.CH: CH,).C,H,.(OH),(OMe)(1, 3, 4).—Ale. sol. 
iat blue-green w. alc. FeCl,. (In ethereal oil from Piper 

etle.) 

Diethyl Acetylsuccinate, C,,H,,0,.—Red-violet color w. FeCl,.— 
Saponification by Test V—2 gives acetic and succinic acids 
and C,H;OH (Tests 311, 320, and 814). 

Isoeugenol, (CH:CH.Me).C,H;.(OH).(1, 3, 4). — Solidifies in 
freezing mixture.—Alc. sol. green w. FeCl. 

{ Ethyl Benzoylacetate, C,H,.CO.CH,.CO,Et.—S. without de- 
composition in c. dil. NaOH.—Ale. sol. gives red-violet color 
w. FeCl,.—Saponification by Test V—2 gives acetophenone, 
C,H,OH and CO, (Tests 712 and 814). 

Phenylacetylacetone, Ph.CH,.CO.CH,.CO.Me.—D. s. c. aq.; e. 8. 
dil. alkalies—AgC,,H,,O,, flocculent ppt. 

Isoamyl Salicylate, o-HO.C,H,.CO,C,H,,.—Saponification by 
Test V gives salicylic ac. and C;H,,OH (Test 319). 

Methyl Orcinyl Ether, MeO.C,H,.OH. — D. s. aq.; e. s. alc. or 
eth.—Browns on exposure to air. 

Ethyl Benzylacetoacetate, C,H,O0.CH(C,H,).CO,Et.—Saponifica- 

tion by Test V—2 gives Me.CO.(CH,),.Ph, C,H,OH, and CO,. 





NUMBERED SPECIFIC AND SEMI-SPECIFIC TESTS FOR 
PHENOLIC COMPOUNDS. 


[TESTS 401-500.] 


401. Ferric-chloride Colorations. 


The test with ferric chloride, forming the first part of Generic Test IV, is designed 
rather to favor the development of a maximum color effect in the largest possible number 
of cases than to secure the most characteristic results for individual species. To obtain 
the ferric-chloride coloration attributed to any phenol in the description given in the tables, 
it is necessary to pay attention both to certain principles that will be now stated, and to the 
special supplementary directions concerning dilution, etc., that form part of many of 
the individual specific descriptions. 

The most desirable concentration for the phenol solution is one that will give a color 
of such quality and intensity that, when viewed horizontally in a six-inch test-tube, it will 
nearly match a spectrum color or ‘‘tint’’, rather than a “shade” or a “broken color” of the 
color standard. ‘This concentration varies greatly with the phenol, but in aqueous solu- 
tions is often met in a 1 per cent solution. Atcohol is usually a much less satisfactory 
solvent in these tests than water, but is sometimes to be preferred. The same phenol often 
gives different colorations in the two solvents. Hot solutions must never be used with 
either solvent. The colors from some phenols are permanent for hours; but more often 
are very transitory, the first coloration sometimes undergoing a complete change in hue, 
or entirely fading away within a few seconds or minutes. The coloration is occasionally 
accompanied by a precipitate. The appearance of a color is prevented by the presence 
of either free acid or alkali, or else its character is essentially modified (cf. pyrocatechin),. 
An excess of ferric chloride may destroy the coloring matter that is first formed, or obscure 
the proper coloration by blending it with yellow. 

The usual procedure in the specific test with ferric chloride is as follows: 

Place 5 cc. of the clear, cold solution of the phenol, which has the concentration speci- 
fied in the tables, in a six-inch test-tube. Add one or more drops of a ferric-chloride solu- 
tion (1 : 40) prepared by diluting one volume of the 10 per cent stock solution of the 
salt with three volumes of water. Use no more of the reagent than is required to produce 
a color suitable for comparison. Shake; and then, without delay, make a careful com- 
parison of the color produced with the color standard. Repeat the comparison after the 
- mixture has stood for five and for fifteen minutes. Comparisons should be made in clear 
diffused daylight, looking horizontally through the tube towards a white wall or card imme- 
diately behind it (cf. p. 232). 


402. The Phthalein Fusion. 

Mix about 0.05 grm. of the phenol with an equal bulk of powdered phthalic anhydride 
in a dry test-tube. Moisten with one drop of concentrated sulphuric acid. Stand the tube 
in a small beaker containing an inch or two of sulphuric acid, oil, or molten paraffin, which 
has been heated up to a nearly constant temperature of 160°. Heat for three minutes. 


Cool. Add 2 cc. of cold water, and 1-2 cc. of sodium-hydroxide solution (1 : 10); i.e. 
107 


108 SPECIFIC TESTS FOR PHENOLIC COMPOUNDS. 


enough to give the solution quite a strong permanent alkaline reaction. Stir the fused 
mass at the bottom of the tube until most of it has dissolved. Dilute with an equal vol- 
ume of water and filter. Compare the color of the filtrate with the color standard (ef. 
p. 232), using such a dilution that the comparison can be conveniently made in a six-inch 
test-tube held before a white background. If the solution shows a fluorescence, examine 
its color with a black background. 

The colors observed in this test are frequently intense and characteristic. When 
the coloration given by a phenol has been compared with the color standard, it will usually 
be found mentioned among the tabulated properties and reactions of the species. 


411. Hydroquinone. (Properties tabulated on p. 99.) 

1. Dissolve 0.1 grm. of the substance in 3 cc. of warm water. Cool, and slowly add 2-3 
cc. of a 10 per cent ferric-chloride solution. Shake. Filter off the precipitate of green-black 
glistening quinhydrone. Collect the filtrate in a small graduate and wash with cold water 
until the total filtrate measures 10 cc. Rinse the precipitate into a test-tube, using 6 cc. 
of water. Warm to just 40°, so as to partly dissolve the crystals. (Boiling would decom- 
pose the quinhydrone to quinone.) Cool to below 20°. Filter into a small graduate, and 
wash with cold water until the filtrate measures 10 cc. Dry the precipitate on a piece of 
porous tile supported over a drying-oven where the temperature will be 35° to 40° for 
twenty minutes, and determine its melting-point. Quinhydrone is obtained in this test 
in slender needles of a peculiar greenish-black color and beautiful metallic luster. Rapidly 
heated it begins to sublime at 145°-50°; gradually softens; and, finally, not far from 170° 
(uncor.) melts completely to a dark orange-red liquid. Even when cold it emits a faint 
pungent odor of quinone. 


412. a-Naphthol. (Properties tabulated on p. 94.) 

1. Dissolve 0.05 grm. of the naphthol in 10 ce. of a 1 per cent caustic-soda solution. 
Add five drops of chloroform, and boil 20 seconds. Compare the color immediately with 
the standard (cf. p. 232). 

a-Naphthol gives at first a clear blue (B). In 15 minutes the color changes to a bluish- 
green (GB-BG); in 4} hours to yellow-green (YG). 

2. Dissolve 0.10 grm. of the substance, and 0.15 grm. of picric acid, in 10 cc. of boiling 
dilute alcohol (1:1). Allow to cool slowly. Filter off the orange (O) needles of picrate, 
which separate after short standing and shaking, and wash with 2 cc. of dilute alcohol 
(1:1). Dry in a warm place on a bit of porous tile. Determine the melting-point in a 
bath whose temperature is rising somewhat rapidly. 

The picrate, (C,,H,O.C,H,(NO,),0), melts at 188.5°-189.5° (uncor.). 


413. @-Naphthol. (Properties tabulated on p. 96.) 

1. Apply Test 412, 1.—The first coloration is blue (B); but unlike that from a-naphthol 
it fades rapidly, passing through GB and YT, of the color standard to colorlessness in 10 
minutes. j 

2. Dissolve 0.10 grm. of the substance, and 0.15 grm. of picric acid, in 6 ce. of boiling 
dilute alcohol (1:1). Then proceed as in Test 412, 2. 

The picrate, (C,,H,O.C,H,(NO,),0), crystallizes in long thin needles of an orange- 
yellow color (YO) which melt, when somewhat rapidly heated, at 155.5°-156.8° (uncor.). 


414. Phenol. (Properties tabulated on p. 91.) 

1. The ‘‘phthalein fusion” (Test 402) gives a bright violet-red (VR) solution after 
adding alkali due to formation of phenolphthalein. 
2. Dissolve 0.05 grm. of the substance in 1 cc. of concentrated sulphuric acid. Pour 
with stirring into a mixture of 1 cc. of concentrated sulphuric acid and 1 ce. of concen-— 
trated nitric acid. Heat on a water-bath for 5 to 10 minutes. Pour slowly into 10 ce. 


SPECIFIC TESTS FOR PHENOLIC COMPOUNDS. 109 


of cold water. Cool thoroughly. Filter. Wash the precipitate with a cold mixture of 
2 cc. of water and 0.5 cc. concentrated hydrochloric acid. Recrystallize from a boiling 
mixture of 4 cc. of water and 1 cc. of concentrated hydrochloric acid. Cool well and filter. 
Wash as before with a cold mixture of 2 cc. of water and 0.5 ec. concentrated hydrochloric 
acid. Dry at 100°, and determine the melting-point. 

The product in this test is picric acid (trinitrophenol) melting at 122.5° (cor.). Picric 
acid crystallizes from the dilute hydrochloric acid in plates, that are at first nearly color- 
less, but which gradually become yellow on exposure to the air. It deflagrates when 
heated on platinum foil. A dilute aqueous solution of the compound stains the skin and 
dyes wool an intense yellow; and its taste is very bitter. The test is simple, and very satis- 
factory when the result is corroborated by other evidence; but it should be remembered 
that picric acid is also formed, though usually not with the same ease, by the nitration 
of some other compounds. Since picric acid can be dried at 100°, this test may be com- 
pleted more quickly than Test 3. It is, nevertheless, at least equally reliable. 

3. Dissolve 0.05 grm. of the substance in 2 ce. of water, and add a saturated aqueous 
solution of bromine until the reagent is present in excess, the color of the liquid then re- 
maining permanently yellow. Filter off the bulky, curdy yellowish-white precipitate. 
Transfer to a small beaker. Cover the precipitate with water, and add acid sodium-sul- 
phite solution gradually until a strong odor of sulphur dioxide remains after stirring and 
warming to 40°. Filter. Wash well with cold water. Dissolve in 15 cc. of boiling 40 
per cent alcohol. Filter off the precipitate which separates on cooling. Transfer to a piece 
of porous tile; allow to become thoroughly air dry, and determine the melting-point. 

The white, crystalline 2, 4, 6-tribromphenol obtained as the final product by this pro- 
cedure is very insoluble in cold water and melts at 92.5°-93.5° (uncor.). The precipitate 
with bromine water contains at first an excess of bromine, and consists of the compound 
C,H,Br,O, which loses one atom of bromine and is converted into the tribrom-derivative 
during the treatment with the sulphite solution. Salicylic acid also gives tribromphenol 
when treated with bromine water. The bromine-water test is most useful when phenol 
is present in small quantity in a dilute aqueous solution. 


415. Phloroglucin. (Properties tabulated on p. 101.) 

Dissolve 0.1 grm in. 1 cc. of concentrated sulphuric acid by stirring. Pour the clear 
solution into a mixture of 1 cc. of concentrated sulphuric, and 1 cc. of concentrated 
nitric acids, cooling with cold water, and stirring until a precipitate appears. Allow to 
stand for five or six minutes; then pour into 10 cc. of cold water. Cool well and filter. 
Wash the precipitate with 2 cc. of water containing 0.5 cc. of concentrated hydrochloric 
acid. Recrystallize from a boiling mixture of 3 cc. of water and 1 cc. of concentrated 
hydrochloric acid. Cool and filter. Wash with 2 cc. of water containing 0.5 cc. of con- 
centrated hydrochloric acid. Dry at 100°-105°. 

The product, trinitrophloroglucin, crystallizes easily in pale-yellow needles melting 
at 165°-166° (uncor.). It stains the skin yellow, and deflagrates when heated on platinum 
foil like picric acid. 

416. Pyrocatechin. (Properties tabulated on p. 94.) 

1. Always apply the ferric-chloride color reaction as directed in the tables, adding 1 cc. 
of the ordinary laboratory sodium-carbonate solution in the latter part of the test. This 
test requires very little substance, and is one of the most satisfactory of its class. 

2. Dissolve 0.05 grm. of the substance in 2.5 cc. of warm chloroform. Add 0.4 ce. 
of bromine. Evaporate to dryness on a water-bath. Dissolve the residue in 5 ce. of cold 
alcohol. Add 20 cc. of cold water. Shake, and then filter. Wash the precipitate with a 
little cold water. Redissolve in 5 ce. of alcohol, and reprecipitate with 20 cc. of cold water. 
Allow the precipitate to become air dry on a piece of porous tile, and determine its melting- 
point. 


110 SPECIFIC TESTS FOR PHENOLIC COMPOUNDS. 


The product, tetrabrompyrocatechin, crystallizes in white needles. As obtained in 
this test, the crystals are often tinged with violet, and melt (not very sharply) at about 
192°-3° (uncor.) after beginning to shrink and soften at 185°-187°, 


417. Pyrogallol. (Properties tabulated on p. 96.) 

1. To 2 ec. of water in a 6-inch test-tube add 1 drop of glycerine and 5 drops of 
a solution of 0.01 grm. of the substance in 1 cc. of water. Next add 2 cc. of concentrated 
sulphuric acid and boil for 20-25 seconds. Then, without delay, compare the color of the 
hot solution with the color standard (cf. p. 232). Use a white background behind the tube. 

The color given by pyrogallol in this test is a clear tint of violet-red (VRT 1-2). On 
continued boiling or standing, the color intensifies rapidly, but soon becomes impure and 
unsuited for purposes of comparison. 

2. In a dry test-tube place 0.1 grm. of pyrogallol, 0.5 grm. of powdered anhydrous 
sodium acetate, and 1.0 cc. of acetic anhydride. Boil for one and one-half to two minutes, 
Add 10 cc. of water, and boil for fifteen or twenty seconds till the oily liquid solidifies, 
Cool. Filter, and wash with 10 cc. of cold water. Dry at 100°-105°. 

The product obtained in this test, pyrogallol triacetate, is in the form of white crys- 
tals which soften at about 155° and melt at 160.5°-161.5° (uncor.) when heated rather 
rapidly. Recrystallization from 4 cc. of strong alcohol raises the melting-point about 0.5? 


418. Resorcin. (Properties tabulated on p. 95.) 

1. One of the simplest, most delicate, and rapid of the tests for resorcin is the fluoresceis 
fusion, which is fully described under Test 318-1. If more convenient, substitute phthalir 
anhydride for the phthalic acid. 

Color reaction 114 with formic aldehyde furnishes another simple resorcin test. 

2. Dissolve 0.1 grm. in 1 cc. concentrated sulphuric acid. Pour slowly with constant 
stirring into a cold mixture of 1 cc. concentrated nitric acid and 1 cc. concentrated sul- 
phuric acid. (It is well to place the mixed acids in a small round-bottomed dish resting on 
the top of a small beaker filled to the brim with very cold tap water.) Do not run in 
the resorcin solution fast enough to cause a permanent brown coloration in the acid. When 
all has been added, remove the dish from the cold water and allow to stand on the table for 
two or three minutes. Then pour the mixture of liquid and yellow crystals that have sepa- 
rated slowly into 10 cc. of cold water, keeping well cooled with running water. Filter. 
Wash with 5 cc. of cold water. Recrystallize from a boiling mixture of 10 cc. of cold 
water, 4 cc. strong alcohol, and 0.4 cc. concentrated hydrochloric acid. Cool well and 
shake. Filter. Wash with 5 cc. of cold water and dry at 100°. 

The product in this test, trinitroresorcin, consists of slightly yellowish crystals of 
melting-point 175° (uncor.). It stains the skin yellow like picric acid. The yield is good. 


419. Thymol. (Properties tabulated on p. 92.) 

1. The colors obtained in the phthalein fusion (Test 402), and described in the tables, 
are quite characteristic. This test should always be applied. 

2. Dissolve 0.1 grm. of the powdered substance in 1 cc. of concentrated sulphuric 
acid. Add with stirring to a mixture of 1 cc. of concentrated nitric, and 1 cc. of concen- 
trated sulphuric acids contained in a very small dish. Allow to stand on the cover of a boil- 
ing water-bath for three or four minutes. Pour into 20 ce. of cold water. Cool well and 
shake vigorously. Filter. Wash the precipitate with 10 cc. of cold water. Crystallize 
from a boiling mixture of 10 cc. water, 4 cc. alcohol, and 0.4-0.6 cc. concentrated hydro- 
chloric acid. Filter. Wash with 5 ce. of cold water. Dry ona piece of porous tile in the 
air, or in a drying-oven below 50°. 

The product in this test is trinitrothymol, melting at 109°-110° (uncor.). The ecrys- 
tals, which are at first nearly colorless, like those of many other nitrophenols, turn lemon- 
yellow after a few hours’ exposure to the air. 


CHAPTER VI. 
GENUS Veo nies 


OF 
SUBORDER I, ORDER I. 
(Colorless Compounds of Carbon, Hydrogen, anid Gayyen.} 


The tables of this genus contain only the most important esters derived from the well- 
known volatile alcoholic compounds enumerated in the table on p. 116. Other esters 
are to be identified through their alcoholic and acidic saponification products by a method 
which will be given in connection with ‘‘ Procedure 2”’ of the generic test. Esters that 
are rapidly saponified by cold alkali, the ester-acids, ester-phenols, and the enolic esters, 
show a behavior with reagents which places them in Genus III or IV with the acids or 
phenols. Finally, a few esters like those of the aromatic diortho-substituted carbonic 
acids, which offer extraordinary resistance to the action of hot alkali, fall in later genera. 


GENERIC TEST V. 


APPLY PROCEDURE 1.—IF THE RESULT IS NEGATIVE, THE COMPOUND DOES NOT 
BELONG TO EITHER GENUS V OR VI. IF IT SHOWS THAT THE COMPOUND 
MAY BE AN ESTER OR ACID ANHYDRIDE, BUT FAILS TO POSITIVELY IDEN- 
TIFY IT WITH ANY SPECIES DESCRIBED IN GENUS V OR VI, PROCEDURE 2 
SHOULD, IF POSSIBLE, THEN BE APPLIED._[PROCEDURE 2 MAY LEAD TO 
THE IDENTIFICATION OF ANY ESTER THAT SAPONIFIES TO AN ALCOHOL AND 
ACID DESCRIBED IN THESE TABLES, WHETHER THE ESTER IS ITSELF MEN- 
TIONED OR NOT, BUT IS LONGER THAN PROCEDURE 1.] 


PROCEDURE 1. 


Weigh out very carefully in a 3-inch lipped weighing tube about 0.1 grm. 
of the substance. Add 2 cc. of a nearly colorless and approximately normal solution 
of sodium or potassium hydroxide in pure strong alcohol from a thin-stemmed 
pipette. The pipette need not be accurately calibrated, but must be used with 
such precautions to ensure uniformity in delivery that the volume of liquid dis- 
charged by it in two successive experiments shall not differ by more than about 
0.005 cc. Stopper the weighing tube tightly with a sound soft cork, which must 
be wired down with a thin copper wire in the manner shown in Figure 3. [The 
wire, after being first doubled, is twisted so as to form a small eye at A. It is then 
drawn tightly around the tube by twisting with pliers at B, and the free ends passed 
over the cork and through the eye. The ends are then seized with the pliers and 
drawn back with sufficient force to slightly imbed the wire at the edges of the cork. 
If the wire is now bent sharply back upon itself, as is shown at C, the stopper will 
be securely held during the subsequent heating.] Place 2 ec. of the same normal 


alkali that was added to the substance in a second tube stoppered like the first. 
, act 


112 ESTERS 


Hang the two tubes from a glass rod by their wires, side by side, in a beaker of 
boiling water, and heat for thirty minutes. Or, better still, thrust the tubes 
through perforated cork stoppers, and heat half an hour at 100° in a bath of the kind 
described on p. 152 and shown in Figure 4. Then wash the contents of each tube 
into a separate small beaker, and titrate carefully with deconormal acid and phe- 
nolphthalein. From the results of the titrations calculate the ‘‘saponification 
equivalent” * of the compound by use of the following formula, in which the 





ge, By 


number of cubic centimeters of standard acid consumed in neutralizing the alkali 
used for the blank experiment is represented by a; and the quantity consumed 
by the alkali after being heated with the substance, by 6. Then— 


1000 X grm. of ester taken 


Sap. Ed.= (py Xnormal strength of the standard acid 


If this equivalent is found to have a value greater than 500, pass on to Genus 
VII; for in this case the compound can not be a species described in either Genus V 
or VI. If, on the contrary, the equivalent has a value less than 500, a search must 
be made through the proper divisions of the tables of Genera V and VI for a species 
whose physical constants and saponification equivalent correspond to those found 
for the substance. If this search leads to the discovery of an apparently corre- 
sponding species, the identification may sometimes be satisfactorily completed by 
the application of special tests suggested in the text. In all other cases, provided 
the supply of substance remaining permits, it is best to saponify a larger quantity, 


* By “saponification equivalent ” is here meant the number expressing how many grams of a 
compound would be required to just neutralize 1000 cc. of normal sodium hydroxide solution in 
a saponification experiment. 


ESTERS 113 


and isolate and identify its acid,* or alcohol, or both, by the methods given under 
Procedure 2. 


PROCEDURE 2. 


Saponify with aqueous alkali as directed below under A. Identify any neutral 
saponification products (alcohols, phenols, or ketones) as directed under B, below, 
and any acid saponification products according to C, p. 116. 


A (Saponification). 


Fit a 250-cc. round-bottomed flask with a clean, sound cork stopper perforated 
to receive the lower end of a return-flow condenser that has been mounted verti- 
cally on a heavy iron stand. 

Introduce about 2 grm. of the substance, accurately weighed, into the flask; 
and then, from a pipette, exactly 50 cc. of an aqueous normal solution of pure 
sodium hydroxide. Next drop in an ebullator-tube to prevent bumping (cf. p. 223) 
and boil briskly for about two hours, or even longer if the odor or appearance of 
the mixture gives indication that, while the substance has been attacked by the 
treatment, a portion of it remains unchanged. The flask should rest lightly on a 
square of iron gauze during the boiling, and the burner flame should be shielded 
from drafts of air; for any pause in the boiling that is more than momentary will 
cause the ebullator capillary to fill, after which such violent bumping may occur 
as to shatter the flask. 

The saponification completed, cool; add two drops of phenolphthalein solution, 
and titrate with normal sulphuric acid without removing from the flask. The 
saponification equivalent may now be calculated from the experimental data by 
substituting in the equation— 

1000 no. grm. ester saponified 


eterno oc. alkali neutralized in saponifio. <normalatrength ofalkal: 


2 B (Examination of the Neutral Saponification Products). 


Drop a fresh ebullator-tube into the flask whose contents have been neutralized 
in the titration mentioned in the last paragraph, and rapidly distil off 40 cc. of 
liquid through an inclined condenser, collecting the distillate in a tall narrow 
graduated cylinder or test-tube. 

During the first part of the distillation, observe whether the distillate is turbid, 
separating into two layers in the recipient, or is clear and apparently homogeneous. 
At the same time make careful note of the odor. (The greater part of the volatile 
alcohols, phenols, and ketones will be contained in the first few cubic centimeters 
of the distillate.) After the distillate has all been collected, if two layers are still 





* The quantity of acid present as sodium salt in the neutral solution after the titration in 
Procedure 1 is so small that its direct identification is only occasionally possible. In such cases 
the procedure, after evaporating the solution to a very small volume and filtering, is identical 
with that described in Section C (p. 116) of Procedure 2. 


114 ESTERS, 


present, close the mouth of the test-tube with the thumb and shake, in order 
to ascertain whether the smaller layer, which will usually have a volume con- 
siderably less than 1.0 cc., can be dissolved in the water present. If a clear 
solution is not obtained, separate the two layers by the aid of a long and very 
thin-stemmed pipette. The aqueous solution is at once used for the lettered tests 
(a) to (i) which follow. The smaller layer, consisting of compounds not readily 
soluble in cold water, is dried, and its boiling-point later determined by the procedure 
given towards the end of paragraph (1). 

(a) Phenol.—If the odor of the distillate suggests the presence of phenol, 
remove 1 cc. of the clear aqueous solution to a 3-inch test-tube and add bromine 
water in excess. If a voluminous white precipitate appears, add to a second 1 ce. 
portion of the distillate one drop of a ferric-chloride solution (1:200). Then, if 
a violet coloration is obtained, phenol is probably present. If more conclusive 
evidence is wished for, apply Specific Test 414-3 to the remaining portion of 
the distillate. 

(b) Allyl Alcohol.—If the odor of the distillate is purely pungent, like horse- 
radish or mustard-oil, allyl aleohol may be present. In this case 1 cc. of the distillate 
will instantly decolorize two or three drops of a saturated aqueous solution of 
bromine. (Allyl alcohol is miscible with water.) 

(c) Isobutyl and the Amyl Alcohols.—If the vapors from the first part of the 
distillate are disagreeable and suffocating, tending to produce coughing when deeply 
inhaled, isobutyl alcohol or an amy] alcohol is likely to be present. These alcohols 
always rise to the surface of the distillate as distinct layers during the first part 
of the distillation, but are miscible on shaking,—isobutyl alcohol easily, the amyl 
aleohols with more or less difficulty. Isolate, dry, and determine the boiling-point 
of the alcohol in the distillate by the method described under test (i). 

(d) Benzyl Alcohol.—If the odor of the distillate is faintly aromatic, and some 
of the oily drops that separate from it sink to the bottom of the recipient but dissolve 
later upon being shaken, benzyl alcohol may be present. Separate from the solution 
by the method of paragraph (1). Determine the boiling-point and finally apply 
Test 812. 

(e) Higher Volatile Fatty Alcohols.—If the distillate contains an upper layer 
whose odor is milder, less suffocating, and more aromatic than that of amyl alcohol, 
and does not dissolve in the aqueous layer after shaking, one of the volatile fatty 
alcohols higher in the homologous series than amyl alcohol should be looked for. In 
this case ‘‘ salt out ” the organic compound directly, by adding 40 grm. of dry potas- 
sium carbonate; mix it with the smaller insoluble layer which separated from the 
original distillate; and then dry and determine the boiling-point as in paragraph (i). 

(f) Methyl Alcohol and other Lower Fatty Alcohols and Ketones.—lIf the dis- 
tillate is a clear solution without layers, and is odorless, or has a mild alcoholic odor, 
remove 2 cc., oxidize with a hot copper spiral, and examine for methyl alcohol by 
Specific Test 819. If no colored ring whatever appears in this test, the distillate 
does not contain any volatile alcohol provided for in this method, or acetone; and 
unless some non-volatile alcohol can be separated from the salts remaining in the 
distilling-flask, the compound under examination must next be sought among the 
species of Genus VI. 


ESTERS. 115 


(g) Acetone and Isopropyl Alcohol.—If no satisfactory reaction for methy] 
alcohol was obtained in (f), but a reddish, yellowish, or brownish ring was noticed, 
remove 1 cc. of the original distillate to a 3-inch test-tube and add; first, two 
drops of the iodine solution (described in Test 801); and then barely enough sodium 
hydroxide (1:10) to Just destroy the brown color of the iodine. The immediate 
appearance of a yellowish-white precipitate of iodoform will indicate the possible 
presence of acetone or isopropyl alcohol.* In case such a precipitate does appear, 
separate out the alcohol or acetone contained in the remaining portion of the 
distillate by the method of paragraph (i), and determine its boiling-point. 

(h) Ethyl Alcohol.—If no iodoform was obtained in (g), heat the same portion 
of solution used in the test to 60°, and add another drop of caustic soda and just enough 
more iodine to give a very faint permanent coloration. If a good precipitate of 
iodoform appears within one minute, and the colored ring in test (f) was a deep 
impure greenish or amber yellow, ethyl alcohol is very probably present. If no 
iodoform separates within a minute, normal propyl and butyl alcohols remain to 
be looked for. In any case, proceed as directed in the following paragraph. 

(i) Identification of n-Propyl and n-Butyl, or other Soluble Alcohols, by Boil- 
ing-point Determination.—Transfer the remainder of the distillate, which will now 
measure at least 30 cc., to a 100-cc. distilling-flask containing 30 grm. of dry 
potassium carbonate. Connect with a condenser, and, when the carbonate 
has dissolved, drop in a fresh ebullator-tube and distil over 15 cc. of liquid, 
collecting in a narrow graduated cylinder or test-tube. Dissolve 15 grm. of 
dry potassium carbonate in the distillate by stirring, cooling with running 
water to prevent loss of alcohol by heating and evaporation. Stopper, and allow 
to stand for at least ten minutes. Insert a thin-stemmed pipette of about 25 ce. 
capacity into the liquid, so that its almost capillary point shall rest lightly on the 
bottom of the tube. Suck the solution, to the last drop, into the pipette. After 
waiting a few seconds for all the small globules of alcohol to rise to the surface and 
unite, allow the lower layer, consisting of carbonate solution, to run out slowly 
into a beaker. Collect the upper layer of alcohol, which may measure less than 
0.5 cc., by itself, in a narrow weighing-tube just wide enough to admit the stem of 
the pipette. Drop in a granule of dry potassium carbonate having a bulk one- 
third as great as that of theliquid. Stopper, and allow to stand for half an hour or 
more. Then incline the tube; remove the clear alcohol by a thin capillary pipette, 
and determine the boiling-point by Siwoloboff’s method, following the directions 
for manipulation given on p. 222. Do not neglect the precaution to boul off half the 
liquid before allowing it to recede into the capillary for the final observation of 
temperature. This method requires no complicated apparatus, and gives useful 
results with as little as 0.1 cc. of an alcohol. Enough alcohol will often be left 
after the boiling-point determination to permit its identification by other special 
confirmatory tests. 

The accompanying table contains a list of all the neutral volatile products that 
are formed from the saponification of the ester species described in the tables of 
Genus V. With the exception of phenol, they are all liquids at the ordinary tempera- 
ture; and with the exception of phenol and acetone, all are alcohols. 


* See Test 801, p. 166. 








116 ESTERS, 














Neutral Saponification Boiling-point| Number of |} Neutral Saponification | Boiling-point | Number of 
Product. COs iSpecific Test. Product. (Cas Specific Test. 
Acetone Ua eyir ens awe 56- 5c. qt er Amy] Alcoho.. . 128-7 
Methyl Alcohol....... 66 819 Isoamyl Alcohol... . 130 
Ethy! Alcohol........ 78-4 814 n-Amyl Alcohol... ./137-8 (th. i.) 
Isopropyl Alcohol. .... 82-8 818 n-Hexyl Alcohol. ... 15/c: 
Tert. Butyl Alcohol. ... 82-9c. n-Heptyl Alcohol. . .{175-8 (th. 1.) 
Allyl Alcohol... 96-6 811 n-Octyl Alcohol... ./195-5 (th. i.) 
Propyl Alcohol........ 97 -4c. 820 Phenol . : 183 414 
Sec. Butyl Alcohol. . 99-8 Benzyl Alcohol. . 204-7c. 812 
Isobutyl Alcohol.. 106-5 817 Glycerinesee eens. 1290 (very lit- 816 
n-Butyl Alcohol. ...... Iife; 813 tle volatile 
with steam) 





(j) Non-volatile Alcohols.—Esters of alcohols not volatile with steam form- 
ing, with the exception of the natural fats, a comparatively unimportant class, 
are omitted from the tables. The alcohols from such esters remain behind in 
the flask with the neutral sodium salts after the distillation in B. They may 
usually be separated from these salts by extraction with ether or other organic 
solvent, and identified, after purification, by application of the usual systematic 
procedure used for the species of Genera IV, VII, and VIII. But unless the 
alcohol in such cases is very easily purified, a much larger quantity of substance 
will have to be used in the saponification than would otherwise be necessary. 

For the identification of glycerine, after saponification, evaporate the neutral 
salt solution to dryness on the water-bath, extract with ether-alcohol, and then 
proceed as directed in Test 816. 


C (Examination of the Acid Saponification Products). 


The acid radicals of esters are identified through an examination of the sodium 
salts remaining in the neutral solution obtained from the saponification equivalent 
determination of A (p. 113) after the alcoholic saponification products have been 
removed by the methods described under B (p. 113). 

This neutral saline solution, if not clear, must first be filtered. Then add to it, 
in the cold, a quantity of normal sulphuric or hydrochloric acid exactly equivalent * 
to the alkali conswmed during the saponification; i.e. Just enough to unite with that 
portion of the sodium present which is in combination with the organic acid. Shake 
vigorously, and then proceed as directed in paragraphs (a), (b), and (c) below. 

(a) Insoluble Acids.—If a precipitate of an insoluble acid appears upon acidifi- 
cation and shaking, filter it off; purify it by recrystallization or other means; and 
identify it by reference to the tables of Genus ITI. 

(b) Soluble Acids Volatile with Steam.—lIf no precipitate appears upon acidi- 
fication, place the solution in a distilling-flask, drop in an ebullator capillary (ef, 
page 223), to prevent bumping, and rapidly distil over al! but about 20 ce. (It 
may be necessary to add more water to the flask and to again distil, if the acid 
should be one that is only slowly volatile with steam.) Examine the distillate 
for soluble volatile acids. 

To identify acetic acid or any of its immediate higher homologues in the same 

* If the mineral acid added at this point, and the alkali used for the saponification, both have 
the same normality, the volume of the standard acid here required will be identical with the 


‘‘cc-alkali neutralized” which appears as a term in the denominator of the equation for the cal- 
culation of the saponification equivalent on p. 113. 


ESTERS. 117 


series, neutralize the distillate exactly with caustic soda, evaporate to dryness, 
and apply Test 311 to the residue. The presence of formic acid in the distillate 
may be established by Test 315. 

(c) Soluble Acids not Volatile with Steam.—Pour the mixture remaining 
in the distilling-flask after the removal of the volatile acids in (b) into an evaporating- 
dish, and evaporate to dryness on the water-bath. Extract the residue with ether or 
other volatile organic solvent. Purify the extracted acid, and identify it by the 
tables of Genus III. 

Observations on Generic Test V. 

The ease with which esters are saponified differs with the species: and the 
method of saponification. Species soluble in water are all readily saponified by 
either Procedure 1 or 2; and some of them, like methyl formate, so rapidly that 
they may be slowly titrated, and are therefore described in Genus III instead of V. 
Among the liquid esters there are some slightly soluble species, like diethyl succinate, 
which appear perfectly neutral in the titration test for acids, but which are dissolved 
with saponification when shaken with cold aqueous normal alkali. Compounds 
of this class escape being classified with the phenols only because of the provision 
that Test IV—2, with alkali, shall not be applied to liquid species. 

With increasing insolubility of the ester in water, saponification by Procedure 2 
becomes slower and more difficult; but as most esters are quite soluble in hot alcohol, 
the rate of saponification of different species by Procedure 1 is comparatively 
uniform, so that the reaction is usually completed within half an hour. Procedure 1 
is on this account an indispensable preliminary generic test for difficultly soluble 
esters. Some insoluble esters of high molecular weight would escape recognition 
as species of Genus V if examined by Procedure 2 only. 

As regards really ‘‘ non-saponifiable esters,” there is no positive evidence that 
such species exist in Order I; and it has been shown by Mr. J. R. Odell, in the 
writer’s laboratory, that even the esters of diortho-substituted aromatic acids, 
which V. Meyer has pointed out are exceptionally alkali resistant, are measurably 
attacked by the treatment of Procedure 1. Methyl 2, 4, 6-Trimethylbenzoate, for 
example, is 7 per cent saponified in the procedure at the end of half an hour, or 
18 per cent when the salting-out effect * of the normal alkali is counteracted by 
previous dilution with an equal volume of alcohol. The velocity of saponification 
with esters of this class is not great enough, however, to bring them into Genus V. 

The most serious limitation of Procedure 1 as a complete generic test is, that 
the use of ethyl alcohol as a solvent renders the direct identification of the lower 
boiling alcohols, when they are formed as saponification products, impracticable. 

The possibilities for experimental error in the determination of a “‘ saponification 
equivalent ” by either of these procedures are more numerous than in the deter- 
mination of the “neutralization equivalent” for acids. Differences of 5 per cent 
between the values found by these methods, and calculated from the theory, should 
not be considered serious discrepancies. ‘The main object of the saponification is to 
ascertain quickly whether a compound really belongs to Genus V or VI or not. 





* Caustic soda appears to produce a “salting-out”’ effect upon some esters in alcoholic solu- 
tion even when its concentration is onlv normal. In such eases the addition of one or two vol- 
umes of alconol will give a clear solution and accelerate the saponification. 


COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER JJ 
GENUS V, ESTERS. 


DIVISION A,—SOLID ESTERS WHOSE NEUTRAL SAPONIFICATION 
PRODUCTS, METHYL, ETHYL, PROPYL, BUTYL, AND ISOBUTYL 
ALCOHOLS, AND PHENOL, ARE SOLUBLE IN COLD WATER AND 
READILY VOLATILE WITH STEAM. 





Melt- 








ing- | Sapon. Boing point ESTERS.—Solid Esters whose Neutral Saponification Products 
faey Equiv. ae: are Soluble in Cold Water and Readily Volatile with Steam. 
Generic Position and Properties of 
the Acidic Saponification Products, 
20 150 21l1c Phenyl Propionate, C,H,,0,— (III, B,1),b.p.140-7°; Test 311. 
22 350 Methyl Behenolate C,.H,,0>. — (III, A, 2), m.p. 57: 5°, 
94.2 | 284 Ethyl Palmitate, C, H,,0,. — ¥e 62-6°¢ 
27-8 176°d.(13mm.)| ‘‘ Bempoyiicere cere) CrHOn 
28 270 Methyl Palmitate, C,,H,,0,.— (III, A,2), ‘*  62-6°c. 
29 253° Triethyl pte I UTS C,,H,,O..— Cf. Genus III, A, 2, 
m. p. 29°. 
29-30 | 366 | a. 360 Ethyl Brassidate, C,,H,,0,.— Ty ye 2) i, Dae ou 
30 ‘«  Tetrinate, C,H,,0,.— 139°; 
32 Diethyl Benzalmalonate, C,,H,.0,.— ‘* 195°; also cine 
namic and malonic acids. 
O07 | 319 224d. Ethyl Stearate, C,,H,,0,.— a ‘f 69°53" c, 
34 180 254 ‘* ~Mandelate, C,,H,.0,.— (IIL, A, 1)" ee 
34 194 273 ‘*  o-Hydrocoumarate, C,,H,,0;.—(III, A, 1), m. p. 82°-3°, 
34 256 ‘* Benzilate, C,,H,,O,— (III, A, 2), a B. 150°. 
34 140 197¢. ‘* Pyromucate, C,H,O,.— (III, A, 1), 132°—4°, 
36 162 260c. Methyl Cinna-nate, C,,H,,0,.— (III, A,2), ‘‘ 133°; Test 313. 
3g | 115 288d Dimethyl Sebacate, C,,H,.0,— (III, A, 1), ‘* 133°. 
38 Methyl Stearate, C,,H;,0,— (III, A,2), ‘‘ 69-3° ce. 
42 149 Diethyl Diphenate, C,.H,,0,.— a ae BOOP: 
43-4 |} 210 295° Ethyl Veratrate, C,,H,,0,.— S ILS tea 
44 196 292 ‘¢  Vanillate, C, ,H,.0,.— Ay oT See 
44 111 Diethyl Terephthalate,C,,H,,0,— ‘‘ sbl. a. 300°; Test 318. 
45-5 | 166 255° Methyl Anisate, C,H, ,0;.— fs m. p. 184-2°, 
48 | 89 230 Dimethyl Tartrate, C,H,,0,— (III, A,1), ‘‘ 168°: Test 314, 
51 204 290 Ethyl 6-Methylcoumarilate, C,,H,,0,.—(III, A, 2), m. p. 188°-9°. 
52 166 Methyl Mandelate, C,H,,0,.— (III, A, 1), m. p. 118°. 
52 119 Diethyl 4-Oxyisophthalate, C,,H,,0;.— (III, A, 2), m. p. 305° 
54 59 163 -3c. } Dimethyl Oxalate, C,H.0,.— Belongs to Genus III, A, 1. 
57 96 abt. 200 Diethyl Mesoxalate, C H.,0, — (TI, A, 1) moti 
57 Ethyl Tikenzylatercaceges C,oH,.0;,—(III, A, 2), m. p. 89°. 
56-8 325-8d. Tetraethyl Ethylenetetracarbonate C,,H,.0,.—Acid unstable. 

59 228 Phenyl Methylethersalicylate, C,,H,,0,.—(III, A, 2), m. p. 98-5°, 
59 196 283 Methyl Veratrate, C, ,H,,0,.— be Mi 9 bo 
59-5 295-297d. | Ethyl meaner ee C,;H,,0;.— Benzoic, acetic, and 

acetone, 








118 


GENUS V, DIV, A. 119 


(ORDER I, SUBORDER I.) 





Melt- 
oe Benen: Boiling-point | ESTERS.—Solid Esters whose Neutral Saponification Products 
Fao) Stade CORSE are Soluble in Cold Water and Readily Volatile with Steam. 








Generic Position and Properties of 
the Acidic Saponification Products, 


61-5 | 127 |207 (16-5 mm.)} Dimethyl Hemipinate, C,.H,,0,.—(III, ie 2),m. p. 161°. 


62-5 | 182 285-7 Methyl Vanillate, C,H, ,0,.— ae cUies 
68 131 324 Diisobutyl Tartrate, CHton — (III, A,1), *‘ 168°; Test 314. 
64-5 | 97 pee Teontitiniates C,H ,,0,.— (III, A, 2), m. p. a. 300°; Test 
68-9 | 198 314c, Phenyl Benzoate, C,,H, ,0,.— (III, ae 2),m. p. 121°; Test 312. 
70 159 Diphenyl Phthalate, C,,H,,0,.— ** 184°; Test 318-1, 
72 166 282 Ethyl m-Oxybenzoate, C,H,,0,.— ‘S ez00. 
72-5 | 224 Phenyl Cinnamate, C,,H,.O,.— a Semlboo Lestalos 
73 480 Ethyl Melissate, C,.H,,0,.— ie sees OC)? 
73 85 Hexaethyl Mellitate, C,,H.,0,..—(III, A, 1), ‘‘ 286°(clos’d tube) 
74-5 | 242 Methyl Benzilate, C,,H,,0;— (III, A,1), ‘‘ 150°. 
75 182 Ethyl 2, 5-Dioxybenzoate, C,H,,0,.— (III, A, 2), m. p. 199°. 
73-8 | 290 Phenyl p-Phenoxybenzoate, C,,H,,0;,.—(III, A, 2),‘‘ 159-5° 
76 305d. Ses ena s-Ethanetetracarbonate, C,,H,.O,.—(III, A, 1), m. p- 
77 186 290 Methyl! $-Naphthoate, C,.,H,,0,. als ae 2), m. p. 184°. 
77-5 | 246 Ethyl Piperate, C,,H,,0,.— he SPAM ip 
78 301-2 Diphenyl Carbonate, C,,H,,0;. 
79 78 285 Trimethyl Citrate, C,H,,O,.—(III, A, 1), m. p. 153°; Test 314. 
79-5 Ethyl Benzosalicylate, C,,H,,0,. 
85 89 282 Dimethyl Racemate, C,H,,0,.—(III, A, 1), m. p. 205°; Test 314. 
85 178 Methyl m-Coumarate, C,,H,,0,.—(III, A,2), ‘* 191°. 
96 95 Dimethyl 4-Oxyisophthalate, C,,H,,0;.—(III, A, 2), m. p. 305°. 
102 72 192 (th. i.) ‘* Fumarate,C,H,0,—  - 3 sbl. 200°. 
102 105 ‘¢  4-Oxyphthalate, C,,H,,0;,— (III, A, 1), m. p. 181°. 
109 | 2909 Phenyl Phenylethersalicylate, C,,H,,O;— (III, A, 2), ‘‘ 113°. 
109 | 258 { Peucedanin, C,,H,,O,.0CH,.—Tasteless, odorless, ndl. from 


Peucedanum officinale. ayy aq.; e.s. h. ale. or ‘eth —tT Mix 
a warm saturated alc. sol. w. an equal vol. conc. HCl and 
boil half a minute. Cool. Wash the white cryst. ppt. w.c. 





alc. Recryst. fr. h. ale. The product of these operations, 
oreoselon, melts at 173° (uncor.). 
iit 198 270-80d. Methyl! a-Anthracenecarbonate, C,,H,,0,.— (III, A, 2), m. p. 206°. 
ise, 135 330 Diphenyl Succinate, C,,H,,0,— (Ill, A, 1), m. p. 185°; Test 320. 
130d. | 121 a Oxalate, C,,H,,0,.— sf poe o> > Testral 
131 152 Methyl p-Oxybenzoate, C,H;0,.—(III, A, 2), m. p. 210°, 
138 | 65-5 Tetramethyl s-Ethanetetracarbonate, C,,H,,0,.—(III, A, 1), m. p. 
169°. 
140 97 Dimethyl Terephthalate, C,,H,,0,.—(III, A, 2), sbl. a. 300°; Test 
318-3. 
158d. | 183 Diethyl Mucate, C,,H,.0,.— aS me pesto 
146 | 164 abt. 330° ‘¢  a-Truxillate, C,,H,,0,.— = ee 4a 
187 71 Hexamethyl Mellitate, C,,H,,0,..— (III, A,1), ‘‘ 286° (closed 
tube). 
192d. | 238 Methyl Gallate+ 3H,0,C,H,,0,— (III, oe 2), ‘*  222°-40°. 


260-70 Ethyl pereityicaroonet C,,H,,03.— of 95°--7°. 


es a 


COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER TJ] 


GENUS V, ESTERS. 


DIVISION B,—LIQUID ESTERS WHOSE NEUTRAL SAPONIFICATION 
PRODUCTS, ETHYL, PROPYL, ISOPROPYL, ALLYL, AMYL AND 
ISOAMYL, BUTYL AND ISOBUTYL, HEXYL, HEPTYL, OCTYL AND 
BENZYL ALCOHOLS, ACETONE, AND PHENOL, ARE READILY 
VOLATILE WITH STEAM. 


Boiling- 


point 
Cape 


32-3 
54-4 
57°5 
68-71 


77 
79-9 


80-3 
81 


82-5 


90-3 


90 - 6c. 


92-3 


98-3 


98-5 


98 - 5c. 


101 
102 


102-3 


103-5 
106-9 


109 - 2c. 


110-1 


Sapon. 
Equiv. 





! 


ESTERS.—Liquid Esters whose Neutral Saponification Products 
are Readily Volatile with Steam. 





Generic Position and Properties of 
the Acidic Saponification Products. 


+ Methyl Formate, C,H,O,.—G. 0-998°/,.—Acid (III, B, 1), b. p. 100-8°; 
Test 315. (Belongs with Acids, Gen. III, B, 1.) 

Ethyl Formate, C,H,0,.—G. 0-938°/,.—Acid (III, B, 1), b. p. 100-8°; 
Test 315. 

t Methyl Acetate, C,H,O,.—G. 0-958°/,.— Acid (III, B, 1), b. p. 118°; Test 
oll; 

Isopropyl Formate, C,H,O,.—G. 0-883(0).—Acid (III, B, 1), b. p. 100-8°; 
Test 315. 

Ethyl Acetate, C,H,0,.—G. 0-924°/,—-Acid (III, B, 1), b. p. 118°; Test 311. 

Methyl Propionate, C,H,0,.—G. 0-937°/,.—Acid (III, B, 1), b. p. 140-79; 
Test 311. 

Methyl Acrylate, C,H,0,.—G. 0-973(0).—Acid (III, B, 1), b. p. 140°. 

Propyl Formate, C,H,O,.—G. 0-918°/,. Acid (III, B, 1), b. p. 100-8°; 
Test 315. 

Allyl Formate, C,H,O,.—G. 0-932(17-5).—Acid (III, B, 1), b. p. 100-8°; 
Test 315. 

Isopropyl Acetate, C,H,,0,.—G. 0-917(0).—Acid (III, B, 1), b. p. 118°; 
Test 311. 

Dimethyl Carbonate, C,H,0,.—G. 1-065(17).—Acid carbonic. 

Methyl Isobutyrate, C,H,,0,.—G. 0-912°/,—-Acid (III, B, 1), b. p. 155°; 
Test 311. 

Ethyl Propionate, C;H,,0,.—G. 0-912(0).—Acid (III, B, 1), b. p. 140-7°; 
Test 311. 

Isobutyl Formate, C;H,,0,.—G. 0-905°/,.—Acid (III, B, 1), b. p. 100-8? 
Test 315. 

Ethyl Acrylate, C,H,0,.—G. 0-939(0).—Acid (III, B, 1), b. p. 140°. 

Methyl Trimethylacetate, C,H,,O,.—Acid (III, A, 1), m. p. 35-5°, 

Propyl Acetate, C,H, ,0,.—G. 0-909°/,.—Acid (III, B, 1), b. p. 118°; Test 
$11. 

Methyl Butyrate, C;H,,0,.—G. 0-919°/,—Acid (III, B, 1), b. p. 162-5°; 
Test 311. 

Allyl Acetate, C;H,O,.—G. 0-938(0).—Acid (III, B, 1), b. p. 118°; Test 311. 

Butyl Formate, C,H,,0,.—G. 0-911(0).—Acid (III, B, 1), b. p. 100-8°; 
Test 315. 

Methyl Ethyl Carbonate, C,H,O,.—G. 1-002(27).—Acid carbonic. 

} Ethyl Isobutyrate, C,H,,0,.—G. 0-890°/,.— Acid (III, B, 1), b. p. 155°; 
aest 311. 

120 


GENUS V, DIV. B. 121 


(ORDER I, SUBORDER I.) 





Boiling- 
point 


O),* be 


116-3 


116-7 
115-20 
118-5 (th. i.) 


119 
119-9 


120-7 
123-3 


124-5 


125 
126 
127-3 
127c. 
128-5 
130-4 


131 (th. i.) 
133-5 
134 (th. i.) 


134-3 
134-7 
136 
139 


141-5 
142 
142-3 
143 
144-5 
148 
148 
149-6 
150 (th. i.) 
150 


151 
151-2 (th. i.) 
152 
153 (th. 1.) 


153-6 


154-5 
155 (th. i.) 


Sapon. 
Equiv. 





ESTERS.—Liquid Esters whose Neutral Saponification Products 
are Readily Volatile with Steam. 





Generic Position and Properties of 
the Acidic Saponification Products. 


| Isobutyl Acetate, C,H,,0,.—G. 0-892°/,.—Acid (III, B, 1), b. p. 118°; 
Test 311. 

Methyl Isovalerianate, C,H,,0,.—G. 0-901°/,.—Acid (II, B, 1), b. p. 176°. 

Ethyl Methacrylate, C,H,,0,.—Acid (III, B, 1), b. p. 162°. 

Cae cece C,H,,0,.—G. 0-875(0).—Acid (III, A, 1), m. p. 
Ethyl Propiolate, C,H,O,.—Acid (III, B, 1), b. p. 144°. 

‘*  Butyrate, C,H,,0,.—G. 0-900°/,— Acid (III, B, 1), b. p. 162-5°; 

Test 311. 

Methyl a-Crotonate, C;H,O,.—G. 0-981(4).—Acid (ITI, A, 1), m. p. 72°. 

} Isoamyl Formate, C,H,,0,.—G. 0-894°/,.—Acid (III, B, 1), b. p. 100-8°; 
Test 315. 

Propargyl Acetate, C,H,O,.—G. 1-005?°/,—-Acid (III, B, 1), b. p. 118°; 
Test 311. 

Butyl Acetate, C,H,,0,.—G. 0-902(0).—Acid (III, B, 1), b. p. 118°; Test 311. 

Diethyl Carbonate, C,H, ,0,.—G. 0-9767°/,—Acid carbonic. 

Methyl Valerianate, C,H,,0,.—G. 0-910(0).—Acid (III, B, 1), b. p. 186°. 

Methyl Methoxyacetate, C,H,O,.—G. 1-089(0).—Acid (III, B, 1), b. p. 203°. 

Ethyl Isoacetoacetate, C,H, 0;—CO, and acetone; Test 711. 

any! Formate, C,H,,0,.—G. 0-902(0).—Acid (IIJ, B, 1), b p. 100-8°; Test 
315. 

Ethyl Methoxyacetate, C,H, 0,.—G. 1-074(0).—Acid (III, B, 1), b. p. 203°. 

Allyl Isobutyrate, C,H,,0,.—Acid (III, B, 1), b. p. 155°; Test 311. 

ziby Methylethylacetate, C,H,,0,.—G. 0-870??/,,.,—Acid (III, B, 1), 

Pp brie 

t Ethyl Isovalerianate, C;H,,0,.—G. 0-885°/,— Acid (III, B, 1), b. p. 176°. 

Methyl Pyruvate, C,H,O,.—G. 1-154(0).—Acid CIII, B, 1), b. p. 165°. 

Ethyl Isocrotonate, C,H, ,0,.—G. 0-927(19).—Acid (IIT, B, 1), b. p. 169°. 

{+ Isoamyl Acetate, C,H,,0,.—G. 0-884(0).—Acid (III, B, 1), b. p. 118°; 
Test 311. 

Ethyl Angelate, C;H,,0,.—G. 0-935(0).—Acid (III, A, 2), m. p. 45°. 

Allyl Butyrate, C;H,,0,.—Acid (III, B, 1), b. p. 162-5°; Test 311. 

Ethyl a-Crotonate, C,H, ,0,.—G. 0-9217°/,— Acid (III, A, 1), m. p. 72°. 

‘¢ Allylacetate, C,H,,0,— Acid (III, B, 2), b. p. 188°. 

‘¢  Valerianatc, C;H,,0,.—G. 0-894(0).—Acid (III, B, 1), b. p. 186°. 
Amy] Acetate, C;H,,0,.—G. 0-896(0) .—Acid (III, B, 1), b. p. 118°; Test 311. 
Methyl Ethoxyaceiate, C,H, ,0,.—G. 1-015(0).—Acid (III, B, 1), b. p. 206°. 

‘¢  Caproate, C;H,,0,.—G. 0-904(0).—Acid (III, B, 2), b. p. 205-7°. 
Ethy] Oxyisobutyrate, C,H,,0;.—Acid (III, A, 1), m. p. 79°. 
aM Lakin beste C,H,,0,—G. 0-898(18).—Acid (III, B, 1), b. p. 
OY fara? 
Ethyl Diethylacetate, C,H, ,0,.—G. 0-883(0).—Acid (III, B, 1), b. p. 190°. 
Methyl Glycollate, C;H,0;..—G. 1- 187(0).—Acid (III, A, 1), m p. 78° 
Ethyl Ethoxyacetate, C,H,,0;.—G. 1-000(0).—Acid (III, B, 1), b. p. 206°. 

‘¢ Methylpropylacetate, C,H,,0,.—G. 0-882(0).—Acid (III, B, 1), b. p. 

eke 


Hexyl Formate, C,H,,0,—G. 0-898(0).—Acid (II, B, 1), b. p. 100-8°: 
est 315. 
Allyl Isovalerianate, C,H. ,0,.—Acid (III, B, 1), b. p. 176°. 
Ethyl a-Ethoxypropionate, C,H,,0;.—G. 0-950(0).—Acid (IIT, B, 1), b. p. 
195°-8°. 








122 GENUS V, DIV. B. 


(ORDER I, SUBORDER I.) 





Boiling- | Sapon. ESTERS.—Liquid Esters whose Neutral Saponification Products 
Poe), Equiv. are Readily Volatile with Steam. 








Generic Position and Properties of 
the Acidic Saponification Products, 





156c- 128 | Ethyl Tiglate, C;H,,0,.—G. 0-926(21).—Acid (III, A, 1), m. p. 64-5°. 
156-9 144 | Isobutyl Butyrate, C,H,,0,.—G. 0-888°/,.—Acid (III, B, 1), b. p. 162-5°; 
Test 311. 
158-9 Ethyl Orthocarbonate, C,H,,0,.—G. 0-925. 
160c. 104 ‘¢  Glycollate, C,H,O;.—G. 1-108(0).—Acid (III, A, 1), m. p. 78° 
160-2 144 | Isoamyl Propionate, C,H,,0,.—G. 0-888°/,— Acid (III, B, 1), b. p. 140-79; 
Test 311. 
161 130 | Ethyl Isobutylacetate, C,H, ,0,.—G. 0-887(0).—Acid (III, B, 2), b. p. 207-7°. 
159-62 128 ‘*  Tetramethylenecarbonate, C,H,,0,.—Acid (III, B, 2), b. p. 195°. 
165 146 | Methyl Oxydiethylacetate, C,;H,,0;—G. 0-990(16-5).—Acid (III, A, 1), 
las jena ie 
165 142 | Ethyl a-Ethylcrotonate, C,H,,0,.—G. 0-920(13).—Acid (III, A, 2), m. p. 
41-5°. 
165 144 | Butyl Butyrate, C,H,,0,—G. 0-888(0).—Acid (III, B, 1), b. p. 162-5°; 
Test 311. 
165 132 | Ethyl a-Oxybutyrate, C,H,,0,.—G. 1-004(0).—Acid (III, A, 1), m. p. 43°. 
166-6 144 ‘«  Caproate, C,H, .0,.—G. 0-889(0).—Acid (III, B, 2), b. p 205-7°. 
168 - 2c. Dipropyl Carbonate, C,H,,0;.—G. 0-949(17) —Acid, carbonic. 


168 - 5c. 160 | Ethyl a-Ethoxybutyrate, C,H,,0,.—G. 0-903(0). 
168-8 158 | Isoamyl Isobutyrate, C,H,,0,.—G. 0-876°/,— Acid (III, B, 1), b. p. 155°; 


Test 311. 
169-2 144 | n-Hexyl Acetate C,H, ,0,.—G. 0-890(0).—Acid (III, B, 1), b. p. 118°; Test 
SLL: 
170: 5c. 118 | Propyl Glycollate, C;H,,0;.—G. 1-064(0).—Acid (III, A, 1), m. p. 78°. 
173 144 | Methyl Oenanthylate, C,H,,0,.—G. 0-887(0) —Acid (III, B, 2), b. p. 223°. 
173-7c. 132 sy Ethyl Oxalate, C,H,0,.—G. 1-156(0).—Acid (III, A, 1), m. p. 99°; 
Test 317. 
175 160 | Ethyl Oxydiethylacetate, C,H,,0,.—G. 0-961(18-7).— Acid (III, B, 2), 
Draped 
175 146 | Ethyl a-Oxyisovalerianate, C;H,,0,.—Acid (III, A, 1), m. p. 83°-6°. 
176-7 144 | Heptyl Formate, C,H,,0,—G. 0-894(0).—Acid (III, B, 1), b. p. 100-8°; 
Test 315. 
es 158 | Ethyl Isoamylacetate, C,H,,O,.—Acid (III, B, 2), ». p. 209°. 
177-5 156 | Isobutyl Angelate, C,H,,0O,.—Acid (III, A, 2), m. p. 45°. 
178 80 Dimethyl Dimethylmalonate, C,H,,0,—G. 1-071(15).—Acid (III, A, 2), 
m, pa lB2>: 
178 160 | Ethyl Acetoxyl-a-propionate, C,H,,0,.—G. 1-046(17).—Acid (III, A, 1), 
mM. p.106_. 
178 - 4c. 130 | Ethyl $-Methoxyisocrotonate, C,;H,,0;,.—G. 1-039(15).—Acid (III, A, 2), 
m. p. 128-5°. 
178-6 158 | + Isoamyl Butyrate, C,H,,0,.—G. 0-882°/,.—Acid (III, B, 1), b. p. 162-5°: 
Test 311. 
179 73 | Methyl Isosuccinate, C,H,,0,—G. 1-107(15).—Acid (III, A, 1), m. p. 135° 
181-5e. 66 ‘¢  Malonate, C;,H,0O,.—G. 1-160(15).—Acid (III, A, 1), m. p. 182°. 
183 172 | Ethyl Dipropylacetate, C,,H,.0,.—Acid (III, B, 2), b. p. 219-5°. 
184 ‘¢ Dimethylacetoacetate, C,H,,0;.—G. 0-991(16).—CO, and isopropyl 
acetone. : 
186-1ce. 73 | + Diethyl Oxalate, C,H,,0,.—G. 1-082(18-2).—For reactions of ester cf. 
page 74. (Belongs in Genus III, B.) 
190 Diisobutyl Carbonate, C,H, .0,.—G. 0-919(15).—Acid, carbonic. 


190 146 | Ethyl a-Oxyvalerianate, C,H,,0,.— Acid (III, A, 1), m. p. 31°. 





GENUS JV, DIV. B. 123 


(ORDER I, SUBORDER I.) 





POMDE: Sapon. ESTERS.—Liquid Esters whose Neutral Saponification Products 
tC). Equiv. are Readily Volatile with Steam. 





Generic Position and Properties of 
the Ac; ic Saponification Products. 


190 158 eee Acetate, C,H, ,0,.—G. 0-874(16).—Acid (III, B, 1), b. p. 118°; Test 
193 158 | Methyl Caprylate, C,H,,0,.—G. 0-894(0).—Acid (III, B, 2), b. p. 237-5°. 
194 172 | f{ Isoamy]l Isovalerianate, C,,H.0,.—G. 0-87(0).—Acid (III, B, 1), b. p.176°. 
195 168 | Ethyl Diallylacetate, C,,H,,0,.—Acid (III, B, 2), b. p. 227° ¢. 
195-2 (th.i.)} 73 pacety! Succinate, C,H,,0,.—G. 1-126(15).—Acid (III, A, 1), m. p. 185°; 
est 320, 


195-5 140 | Ethyl Sorbate, C,H,,0,.—Acid (III, A, 2), m. p. 134-5°. 
196 (sl. d.)} 63 | Dimethyl Acetylenedicarbonate, C,H,O,.—Acid (III, A, 1), m. p. 178°-9°. 


196 136 | Phenyl Acetate, C,H.O,.—G. 1-093°/,— Acid (III, B, 1), b. p. 118°; Test 311. 
196 Ethyl Ethyleneacetoacetate, C,H,,0;.—G. 1-048(15).—CO, and acetopro- 
pyl alc. 
196-5 94 | Diethyl Dimethylmalonate, C,H,,0,.—G. 1-002(15).— Acid (III, A, 1), 
m, p.-192-. 
198 87 | Diethyl Isosuccinate, C,H,,0,.—G. 1-021(15).—Acid (III, A, 1), m. p. 135°. 
198c. 80 | + ‘‘ Malonate, C,H,,0,.—G. 1-077(0).—Acid (III, A, 1), m. p. 132°. 
198 158 | Octyl Formate, C,H, ,0,.—G. 0-893.—Acid (III, B, 1), b. p. 100-8°; Test 315. 
199¢c. 136 | + Methyl Benzoate, C,H,O,.—G. 1-103(0).—Acid (III, A, 2), m. p. 121°; 
Test 312. 
199 Ethyl a-Propionylpropionate, C,H,,0;—G. 0-995(0).—CO, and diethyl 
ketone. 
200-5 (th. i.) Ethyl Methylethylacetoacetate, C,H,,0,—G. 0-947”/,;.;—CO, and sec, 


butyl acetone. 
203-7 172 | n-Amyl Valerianate, C,,H,,.0,.—G. 0-881(0).—Acid (II, B, 1), b. p. 186°. 
200-5 Diethylacetylacetone, Me.CO.C.Et,.CO.Me.—Acid (III, B, 1), b. p. 118° and 
diethylacetone. 
204-5 170 | Isoamyl Tiglate, C,,H,,O,—Acid (III, A, 2), m. p. 64-5°. 
205c. 144 | Ethyl Levulinate, C;H,,0,—G. 1-033(0).—Acid (III, B, 1), b. p. 239°. 
205 (th. i.) | 72 | Dimethyl Maleate, C,H,O,—G. 1-153(14).—Acid (III, A, 1), m. p. 130°. 


205-1 172 | Hexyl Butyrate, C,,H,,0,—G. 0-883(0).—Acid (III, Brel) bape lozane: 
Test 311. 
206c. 79 | Dimethyl Mesaconate, C;H,,0,.—G. 1-136(4).—Acid (III, A, 1),m. p. 202°. 
206 150 | Benzyl Acetate, C,H,,0,.—G. 1-057(16-5).—Acid (III, B, 1), b. p. 118°; 
Test 311. 
207 94 | Diethyl Ethylmalonate, C,H,,C,.—G. 1-008"*/;;—Acid (III, A. 1), m. p. 
Le 5, 
207°5 101 | Diethyl Methylethylmalonate, C,,H,,0,.—G. 0-994(15).—Acid (III, A, 1), 
evn Neyga eae 
207°5 172 | Ethyl Caprylate, C,,H,,0..—G. 0-887(0).—Acid (III, B, 2), b. p. 237-5°. 
207 -7c. Dibutyl Carbonate, C,H,,0,.—G. 0-941(0) .—Acid, carbonic. 
208-2c. | 80 | Methyl Ethyl Succinate, C.,H,,0,—G. 1-093(0).—Acid (III, A, 1), m. p. 
185°; Test 320. 
208 Ethyl a-Butyrylpropionate, C,H, ,0;.—G. 0-988(0). 
210 172 ‘¢” Mesitonate, C,H,,0,.—Acid (III, A, 1), m. p. 74°. 
210 172 | n-Octyl Acetate, C,,H,.0,—G. 0-885(0).—Acid (III, B, 1), Datevins: 
Test 311. 
210-5 79 | Dimethyl Citraconate, C;H,,0,—G. 1- 121(15).—Acid (III, A, 1), m. p. 80°. 
211c 150 | Phenyl Propionate, C,H,,0,,—G. 1 -054(15).—Acid (III, B, 1), b. p. 140-7°; 
Test 311. 
210-2-5 Methyl Itaconate, C,H, ,0,.—G. 1-140(14.7) .—Acid (III, B, 1), b. p. 161°. 





212c. 150 | } Ethyl Benzoate, C,H, ,0,,—Acid (1H, Ap2), mp. 121°> Test 3iZ. 
cae es ted eli et se ENT SEE 





124 


Boiling- 
point 
(CEA 


213-5 (th. i.) 


213 


213-4 


213*5c. 


214 


214 (th. i.) 


214 (th. i.) 


216 


216-5ce. 


215-20 
217-5 
218 


218-5c. 


220 
221 


221 


221 (th. i.) 


221 
221-5 


220-3 


222- 5c. 


223 


223°5 
222-5 
223-6 


225 (th. i.) 


225 


225-6d. 
226-5 


226-8 


225-30d. 
227-5 (th. i.) 


227-5 
227 - 8c. 


Sapon. 
Equiv. 


172 
93 


101 


82 


150 


168 
85 


87 


186 


86 
150 


101 


176 
108 


164 
101 


108 
100 


108 


186 
88 
101 


86 
108 


100 
164 
148 
186 


93 


GENUS’ V,, DIV. B. 


(ORDER I, SUBORDER I.) 





ESTERS.—Liquid Esters whose Neutral Saponification Products 
are Readily Volatile with Steam. 


Generic Position and Properties of 
the Acidic Saponification Products, 


Methyl Pelargonate, C, .H.,,0,.—G. 0-892(0).—Acid (III, B, 2), b. p. 253°-4°, 
Diethyl Ethylenemalonate, C,H,,0,.—G. 1-065(15).—Acid (III, A, 1),m. p, 
140°. 


Diethyl Isopropylmalonate, C,,H,,0,—G 0-997?°/,,.—Acid (III, A, 1), m. p. 
Bis 


Dipropyl Oxalate, C,H,,0,—G. 1-038(0).—Acid (III, A. 1), m. p. 99°; 
Test 317. 

Ethyl Methylpropylacetoacetate, C,,H,,0;.—G. 0-959(15).—CO, and methyl 
propyl acetone. 


p-Cresyl Acetate, C,H,,O,.—G. 1-066°/,.—Acid (III, B, 1), b. p. 118°; Test 
SB 


Ethyl Pyrotritarate (Uvate), C,H,,0,— Acid (III, A, 2), m. p. 135°. 

Diallyl Oxalate, C,H,,0,—G. 1-055(15-5).—Acid (III, A, 1), m. p. 99°; 
Test 317. 

+ Diethyl Succinate, C,H,,0,—G. 1-072(0).—Acid (III, A, 1), m. p. 185°; 
Test 320. 

Isoamyl Isobutylacetate, C,,H,.0,.—Acid (III, B, 2), b. p. 207-7° ¢. 

Ethyl Isobutylacetoacetate, C, ,H,,03.—G. 0:951(17-5).—Cf. Genus IV, B. 

‘¢  Diethylacetoacetate, C,,H,,0;.—G. 0-974(20).—CO, and diethyl ace- 

tone. 

Diethyl Fumarate, C,H,,0,.—G. 1-063(10).—Acid (III, A, 2), sbl. 200°. 

Methyl Phenylacetate, C,H,,O,.—G. 1-044(16).—Acid (III, A, 2), m. p. 
76-5. 

Diethyl Propylmalonate, C,,H,,0,—G. 0-993(15).—Acid (III, A, 1), m. p. 
96°. 


Methyl a-Phenylpropionate, C,,H,,0,.—Acid (III, B, 2), b. p. 264°. 

Diethyl Methylisopropylmalonate, C,,H,,0,.—G. 0-990(15).—Acid (III, A, 
1), m, p. 124°. 

Ethyl o-Toluate, C,, 

Diethyl(mal.)s-D paninyiedecumaee C,)H, ,0,. 
1); m. p. 129°. 

Diethyl Methylpropylmalonate, C,,H.0,.—Acid (III, A, 1), m. p. 106°. 
es Allylmalonate, C,)H,,0,—G. 1-014(15).—Acid (III, A, 1), m. p. 
103°. 

Diethyl Diethylmalonate, C,,H.»0,—G. 0-992(15).—Acid (IIT, A, 1), m. p. 
iW 


H,,0,.—Acid (III, A, 2), m. p. 102°. 
—G. 1-022(0).—Acid (III, A, 


Methyl Caprate, C,,H,.0,.—Acid (III, A, 2), m. p. 31-3°. 
Diethyl Tartronate, C,H,,0,.—Acid (III, A, 1), m. p. 185°-7°, 
a} Etnylsuccinate, C,,H,,0,.—G. 1-030(21).—Acid (ITT, A, tye. 
98°. 
Diethyl Maleate, C,H,,0,.—G. 1-074(15).—Acid (III, A, 1), m. p. 130°. 
as Isobutylmalonate, C,,H,,0,—G. 0-983(17).—Acid (III, A, 1), m. 
M10 ce2 
Dane Fumarate, C,,H,,0,.—Acid (III, A, 2), sbl. 200°. 
Ethyl Tranetheleneaceroater C,H,,0;.—G. 1-070(15).—M. p. +9°— 
Acid CLAS 2yemrpoia. 
Ethyl m-Toluate, C,,)H,,0,.—Acid (III, A, 2}, m. p. 110-5°. 
‘¢ @G-Dioxybutyrate, C,H,,0,.—Acid (ITI, A, 1), m. p. 74°-5°. 
‘¢  Pelargonate, C,,H,.0,.—G. 0-866(17-5). Acid (III, B, 1), b. p. 253°, 
‘¢  Tsoamylacetoacetate.—Cf. Genus IV, A. 
Diethyl Itaconate, C,H,,0,.—G. 1-050(15).—Acid (III, A, 1), m. p. 161°. 


GENUS V, DIV. B. : 125 


(ORDER I, SUBORDER I.) 





a ——- 


Boiling- | Sapon. ESTERS.—Liquid Esters whose Neutral Saponification Products 
fost Equiv. are Readily Volatile witn Steam. 





Generic Position and Properties of 
the Acidic Saponification Products, 


228 178 | Methyl Ethylphenylacetate, C,,H,,0,.—Acid (III, A, 2), m. p. 42°. 
228 164 | Ethyl p-Toluate, C,,H,,0,.—Acid (III, A, 2), m. p. 176°-7°. 
228 166 |! Methyl Methylethersalicylate, C,H,,O;.—Acid (III, A, 2), m. p. 98-5°. 
228 - 3c. 94 | Dipropyl Malonate, C,H,,0,—G. 1-027(0).—Acid (III, A, 1), m. p. 132°. 
228 -7c. Diisoamyl Carbonate, C,,H,.0;.—G. 0-912(15).—Acid, carbonic. 
229 (th.i.) | 93 | Diethyl Mesaconate, C,H,,0,—G. 1-060(4). Acid (III, A, 1), m. p. 202°. 
229 101 arcu) Oxalate, C, H1,0,-—G. 1-002(14).—Acid (ITI, A, 1), m. p. 99%; 
est 317. 
229c. 164 | Ethyl Phenylacetate, C,,H,,0,.—G. 1-086(16).—Acid (III, A, 2), m. p. 76-5°. 
229- 5c. 150 SrOPy apts C, >H120,—G. 1-032(16).—Acid (III, A, 2), m. p. 121°; 
est - 
230 162 | Allyl Benzoate, C,,H,,O,.—Acid (III, A, 2), m. p. 121°; Test 312. 
230 178 | Ethyl a-Phenylpropionate, C,,H,,0,— Acid (III, B, 2), b. p. 264°. 
231 93 | Diethyl Citraconate, C,H,,0,.—G. 1-047(15).—Acid (III, A, 1), m. p. 80°. 
231 188 | Ethyl a-Oxycaprylate, C,,H,.0,.—Acid (III, A, 2), m. p. 69-5°. 
230-5 101 | Diethyl iS eteong ek ear C,)H,,0,.—G. 1-0138(0).—Acid (III, A, 
2),m: p. 195°. 
232 190 | Methyl a-Methylhydrocinnamate, C,,H,,0,.—Acid (III, A, 2), m. p. 37°. 
233-5 (th.i.)| 108 | Diethyl Butylmalonate, C,,H,.0,—G. 0-988(15).—Acid (III, A, 1), m. p.76°, 
235 180 | Ethyl Methylethersalicylate, C,,H,,0,.—Acid (III, A, 2), m. p. 98-5°. 
235-6 ‘« Dipropylacetoacetate, C,,H,.0,—G. 0-959°/,—CO, and dipropyl- 
acetone. 
237 res a pete Besoate: C,,H,,0,.—G. 1-002(15).—Acid (III, A, 2), m. p. 121°; 
est. olZ. 
237c. 94 | Diethyl Glutarate, C,H,,0,—G. 1-025(21).—Acid (III, A, 1), m. p. 97-5°. 
236-8 93 if Glutaconate, C,H,,0,.—Acid (III, A, 1), m. p. 132°. 


237-8 178 | Ethyl m-Tolylacetate, C,,H,,0,—\G. 1-018(17-5).—Acid (III, A,2),m. p.61°. 
236-40 108 | Diethyl Isopropylsuccinate, C,,H.0,—Acid (II, A, 1), m. p. 117°. 
238-5 176 | Methyl Hydrocinnamate, C,,H,,0,.—G. 1-047(0).—Acid (III, A, 2), m. p. 


48-7°. 
240 178 | Ethyl p-Tolylacetate, C,,H,,0,.—Acid (III, A, 2), m. p. 91°. 
240 168 ‘* Cuminate, C,,H,,0,.—Acid (III, A, 2), m. p. 116-5°. 
40 sl. d. Diethyl Diglycollate, C.H,,0;,—Acid (III, A, 1), m. p. 148°. 
240 120 $a Diallylmalonate, C,;H0,.—G. 0-996'*/,;.— Acid (III, A, 1), 
m. p. 133°. 
239-41 Ethyl Dialiylacetoacetate, C,,H,,0,.—G. 0-948?°/,,.;.—CO, and diallyl ace- 
tone. 
241 178 | Ethyl 1 3-Dimethylbenzoate, C,,H,,0,.—Acid (III, A, 2), m. p. 166°. 
241 115 | Diethyl Isoamylmalonate, C,,H,,0,.—Acid (III, A, 1), m. p. 93°. 
243 -4c. 101 | Dibutyl Oxalate, C,,H,,0,.—G. 1-010(0) .—Acid (III, A, 1), m. p. 99°; Test 
317 
244 200 | Ethyl Caprate, C,,H,,0,.—G. 0-862.—Acid (IH, A, 2), m. p. 31-3°. 
245 180 | Methyl Ethylethersalicylate, C,)H,,0;.—Acid (III, A, 2), m. p. 19-4°. 
245 101 | Diethyl Adipate, C,,H,,0,.—Acid (III, A, 2), m. p. 153° ¢. 
247-1c. 101 | Diisopropyl Succinate, C,H,,0,.—G. 1-019(0).—Acid (III, A, 1), m. p. 185°; 
Test 320. 
247-3c. 178 | Butyl Benzoate, C,,H,,0,.—G. 1-000(20).—Acid (III, A, 2), m. p. 121°; 
Test 312. 


— 247-9e. 178 | Ethyl Hydrocinnamate, C,,H,,0,.—G. 1-034(0).—Acid (ITT. A, 2), m. p 
48-7°. 








126 


Boiling- 
point 
(C.°). 





248 
249-5 
250 -8c. 


249-52 
251 
250-3 


251-5c. 
255 


256-7 


259 
261 


263 

263 

265 
265c. 
265-7 


269 
269 - 5c. 
270 
270-5 
271 


272 
275 


275 
276d. 


278 -3d. 
280 
282 

282-6 


284 (th. i.) 
285 


285-5 


t——~ — . 


Sapon. 
Equiv. 





210 
99 
161 


107 


194 


108 
85 


178 


212 
192 


194 
115 
120 
115 
226 


228 
180 
208 
72 
176 


206 
ey, 


86 
224 


82 
103 


oF 

115 
175 
Pet 


128 


GEN US. Vo tDhV a 


(ORDER I, SUBORDER I.) 





ESTERS.—Liquid Esters whose Neutral Saponification Products 
are Readily Volatile with Steam. 





Generic Position and Properties of 
the Acidic Saponification Products. 


Methyl Undecylenate, C,,H,.0,.—Acid (III, A, 2), m. p. 24-5°. 

Diallyl Succinate, C,,H,,0,— Acid (III, A, 1), m. p. 185°; Test 320. 

Dipropyl Succinate, C,,H,,0,.—G. 1-016(4).—Acid (III, A, 1), m. p. 185°; 
Test 320. 

Diethyl Pentamethylenedicarbonate, C,,H,,0,—Acid (III, A, 2), m. p. 
159°-60°. 

Ethyl Ethylethersalicylate, C,,H,,0O;—G. 1-101.—Acid (III, A, 2), m. p. 
19-4°, 

Ethyl Diisobutylacetoacetate, C,,H,,0;,—G. 0-947(10).—CO, and diisobuty] 
acetone. 

Dibutyl Malonate, C,,H,.0,.—G. 1-005(0).—Acid (IIT, A, 1), m. p. 132°. 

Diethyl i-Malate, C,H,,0;—G. 1-1247'/,—Acid (III, A, 1), m. p. 133°; 
Test 314. 

Ethyl Benzoylformate, C,,H,,O,.—G. 1-121(17-5).—Acid (III, A, 1), m. p. 
65°-6°. 


Ethyl Undecylenate, C,,H,,0,.—G. 0-883(15).—Acid (III, A, 2), m. p. 24-5°. 

Isoamyl Benzoate, C,,H,,0,.—G. 1-004(0).—Acid (III, A, 2), m. p. 121°; 
Test 312. 

Ethyl m-Ethoxybenzoate, C,,H,,0,.—G. 1-088(0).—Acid (III, A, 2), m. p. 
Vic. 


Diisoamyl Oxalate, C,,H,.0,—G. 0-968(11).—Acid (III, A, 1), m. p. 99°; 
Test 317. 

Dimethyl Camphorate, C,,H.0,—G. 1-075?°/,— Acid (III, A, 2), m. p. 
L802 7 

Diisobutyl Succinate, C,.H,.0,.—G. 0-974(15),—Acid (III, A, 1), m. p. 185°; 
Test 320. 

Isoamyl Orthoformate, C,,H,,0,—G. 0-864(23).—Acid (III, B, 1), b. p. 
100-8°; Test 315. 

Ethyl Laurate, C,,H,,0,.—G. 0-867(19).—Acid (III, A, 2), m. p. 43-6°. 

‘*  Anisate, C,)H,,0,.—Acid (III, A, 2), m. p. 184-2°. 

Isoamyl Salicylate, C,,H,,0;—Cf. Genus IV, B; Test 319. 

Trimethyl Aconitate, C,H,,O,.—Acid (III, A, 1), m. p. 191°. 

} Ethyl Cinnamate, C,,H,,0..—G. 1-066(0).—Acid (III, A, 2), m. p. 133°; 
Test 313. 

n-Hexyl Benzoate, C,,H,,0,.—G. 0-999(17).—Acid (IIT, A, 2), m. p. 121°; 
Test 312. 

Diisopropyl Tartrate, C,)H,,O,.—G. 1-13(20).—Acid (III, A, 1), m. p. 168°; 
Test 314. 

Triethyl Aconitate, C,,H,,0,.—G. 1-074(14).—Acid (III, A, 1), m. p. 191°. 

Ethyl Camphocarbonate, C,,H..0;.—G. 1-0567°/,— Acid (III, A, 2), m. p. 
128°, 


Triethyl Ethenyltricarbonate, C,,H,,O,.—G. 1-095*°/,—Acid (III, A, 1), 
mapas ec 

Diethyl{ + ]Tartrate, C,H,,0,.—G, 1-206(20).—Acid (III, A, 1), m. p. 168°; 
Test 314. 

Dimethyl Phthalate, C,,H,,.0,.—Acid (III, A, 2), m. p. 184°; Test 318-1. 

Diethyl Suberate, C,,H,,0,.—G. 0-985(15).—Acid (III, A, 2), m. p. 140°. 
‘¢  Carbopyrotritarate, C,,H, ,0,.—Acid (III, A, 2), m. p. 230°-1°. 
‘« Isophthalate, C,,H,,0O,.—Acid (III, A, 2), m. p. a. 300°; Test 
318-2. 

Diethyl Camphorate, C,,H,,0,.—G. 1-029(16).—Acid (III, A, 2), m. p. 
180° c. 





Boiling- 
poin 


(G.7). 


290 
291-2 
294 


295c. 


295 
298-5 


295-305 
305 
307-8 
308 
308-9 
309c. 
308-5-11 
310 (th. i.) 


314 
323-4c. 


a. 360 





Sapon 
Equiv. 





122 
92 


111 


256 
258 


86-7 
234 
129 
212 
200 
200 
284 
166 


226 
212 


228 





GENUS V, DIY. B. 127 


(ORDER I, SUBORDER I.) 





ESTERS.—Liquid Esters whose Neutral Saponification Products 
are Readily Volatile with Steam. 





Generic Position and Properties of 
the Acidic Saponification Products 


Methyl £-Benzoylpropionate, C,,H,,0;.—Acid (III, A, 2), m. p. 116°. 
Diethyl Azelate, C,,H,,0,.—G. 0-991°/,.—-Acid (III, A, 2), m. p. 106°. 
Triethyl Citrate, C,,H..O0,—G. 1-137?°/,—Acid (III, A, 1), m. p. 153°; 
Test 314 
{ Diethyl Phthalate, C,,.H,,0,—G. 1-118?°/,.—Acid (III, A, 2), m. p. 184°; 
Test 318-1. 
Ethyl Myristate, C,,H,.0,.—Acid (III, A, 2), m. p. 53-8°. 
Diisoamyl Succinate, C,,H,,0,—G. 0-961(13).—Acid (III, A, 1), m. p. 
185°; Test 320. 
Triethyl Tricarballylate, C,,.H,.O,.—Acid (III, A, 1), m. p. 166°. 
Octyl Benzoate, C,,H..0,.—Acid (III, A, 2), m. p. 151°; Test 312. 
+ Diethyl Sebacate, C,,H,,0,.—G. 0-965(16).—Acid (II, A, 2), m. p. 133°. 
Methyl o-Phenylbenzoate, C,,H,,0,.—Acid (III, A, 2), m. p. 110°-1°. 
Ethyl @-Naphthoate, C,,H,,O,.—Acid (III, A, 2), 1. p. 184° ¢. 
‘< —a-Naphthoate, C,,H,,0,.—Acid (III, A, 2), m. p. 160°. 
‘<  Diheptylacetate, C,.H,,0,.—Acid (III, A, 2), m. p. 26°-79- 
eee tpea cus acetate, C,H,,0,.—G. 1-195°7,.—Acid (IIT, A, 1), m. p. 


Etbvl o-Phenylbenzoate, C,,H,,O,.—Acid (III, A, 2), m. p. 110°-1°. 

Benzyl Benzoate, C,,H,,0,.—G. 1-114(18-5°).—Acid (III, A, 2), m. p. 121°; 
Test 312. 

Methyl Phenylethersalicylate, C,,H,,0,.—Acid (III, A, 2), m. p. 117° 


CHAPTER VIIL 
GENUS VI. ACID ANHYDRIDES AND LACTONES 


OF 
SUBORDER I, ORDER I. 


(Colorless Compounds of Carbon, Hydrogen, and Oxygen.) 


To this genus belong all species of the suborder, which, while not attacked 
rapidly enough by cold alkali to give Tests III or IV, yield a saponification equiva- 
lent of less than 500 in Test V, and form the sodium salt of an acid as their sole 
organic saponification product. No independent Generic Test VI exists, the claim 
of any species to membership in the genus being settled by the outcome of the exam- 
ination of the reaction products obtained in Test V (p. 111). 

The number of important species described under Genus VI is smaller than for any 
other genus in Order 1. It has already been mentioned elsewhere that many of the 
simpler and more important anhydrides, like acetic, benzoic, and succinic, and phthalid, 
are sufficiently reactive towards either cold decinormal or normal alkali to be entitled to 
positions with the acids or phenols. The number of species which might otherwise have 
established a valid claim for admission to the genus has been still further diminished by 
the difficulties that lay in the way of procuring pure preparations of representative types 
for direct examination, and the utter impossibility of drawing safe conclusions, a priori, 
as to the behavior of many of them towards alkali from the vague or conflicting statements 
that may be gleaned from a study of their literature. These unavoidable omissions, which 
can only be remedied by later investigations, consist almost exclusively of rare and unim- 
portant compounds. The fact that Genus VI is a skeleton genus to a greater extent 
than most others, has, therefore, little practical significance, except to the investigator 
in a few special fields. 


128 


COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I]. 
GENUS VI, ACID ANHYDRIDES AND LACTONES 


DIVISION A,—SOLID ACID ANHYDRIDES AND LACTONES WIIICH 
DO NOT NEUTRALIZE COLD SODIUM HYDROXIDE SOLUTIONS 
READILY ENOUGH TO GIVE TESTS III OR IV, 2. 





Melting-point 
fU je | 


25 


63-4 


64 
67 


71-7 
73 


86-7 
102-5 
103-5 

128 


128-30 
134 
160-61 


169-70 


218c. 


Rea antenna a 


ACID ANHYDRIDES AND LACTONES.—Colorless and Solid. 


Melilotic Anhyd., 0-0.(.C,H,.C,H,.CO.).—B. p. 272°.—Odor like vanilla grass or 


Tonka bean !—S. c. aq.; d. s. h. aq.; e. s. CHCl,.—Boiled w. alkali gives 
melilotic ac., m. p. 82°-3°.—Br, substitutes in CS, sol. giving compound 
w. m. p. 106° (pr. fr. CHCl,). 

3-Methoethylol(3’)-heptanon(6)-olid(1, 3’),C,,H,,0;—B. p. 330°.— (An _ oxid. 
product of pinene, etc.).—Cryst. v. e. fr. h. aq.; s. aq.; v. s. CHCl,; much 
less s. eth.—Sodium hydroxide and Br added to aq. sol. give CBr,—Neut. 
equiv. 184. 

Palmitic Anhyd., (C,,H;,0),.0. 


+ Coumarin, o-O(.C,H,.C,H,.CO.).— Fragrant odor like vanilla grass or Tonka 
bean !—B. p. 290°-0-5°.—Alm. i. c. aq.; s. h. aq.; e. s. ale. or eth.—Does 
not give Test III or IV.—Test V gives coumaric ac. !—The solution in alkali 
has a peculiar greenish-yellow color !—Adds Br, in CS, sol. (Cryst. fr. alc., 
m. p. 105°.) 

Stearic Anhyd., (C,,H,,0),.0. 


+ Phthalid. o-O(.CH,.C,H,.CO.).—B. p. 290° (th. i.).—Ndl. fr. h. aq.; v. d.s. ¢. 
aq.; e. s. alc.—Alkaline KMnO, gives phthalic acid (Test 318-1) easily.— 
Test V gives o-Oxymethylbenzoic ac. (III, A, 2), m. p. 120°._{Finely 
powdered dissolves after shaking 1-2 min. in Test I1V-2, and so properly 
belongs in Genus IV.]! 


Glycolid, C,H,O,.—_Lft. fr. alc., d. s. c. ale. or eth.; v. s, acetone.—Protracted 
boiling w. aq. gives glycollic ac. 
Meconine, C,,H,,0,. (from mother-liquors of opium alkaloids).—Sbl. in lus- 

trous ndl.—(Cf. Genus III, A, 2.) 


Benzoylperoxide, (PhCO),.0,.—Rhomb. cryst., e. s. eth. or bz.—Explodes on 
heating !—Boiled w. KOH sol. gives benzoic ac. (Test 312) and oxygen. 


Lactid, C,H,O,.—Cryst. fr. h. alc., alm. i. c. aq.— Boiled w. aq. gives lactic ac.— 
(Cf. Genus III, A, 2.) 


Glycollic Anhyd.—Powd. i. aq.—(Cf. Genus ITI, A, 2.) 
Benzoin.—Slightly attacked in Test V.—(Cf. Ketones, VII, A.) 


Saccharin, C,H,,0,.—Pr. of bitter taste. 100 pt. aq. at 15° dissolve 13 pt.—Opt. 
act.[+]; salts however [—].—Ether extracts fr. strongly alk. sol. in Na,CO,.— 
Aq. sol. boiled w. CaCO, gives soluble uncryst. Ca saccharate.—Gives Test 
801! 

Santonin, C,,H, .0,.—Cryst., s. in 5000 pt. c., or 250 pt. h. aq.; s. ¢. alc.; d.s.c.eth.; 
e. s. CHCl,.—Opt. act.—Cryst. rapidly turn yellow in air!—Does not redden 
litmus.—Alcoholic KOH colors red !—Warming w. alkali gives santonic ac. 


+ Cantharidin, C,,H,,0,.—Well-formed cryst., alm. i. c. or h. aq.; v. d. s. ale. 
or eth.—Alc. sol. placed on skin quickly produces painless blisters !—2 pt. 
heated at 100° for 15 min. w. 3 pt. phenylhydrazine hydrochloride, 4-5 pt. 
NaAc, and 30 pt. aq. gives a hydrazonehydrate cryst. fr. ale. w. m. p. 194° c. 
—y Test V gives sodium cantharidate. The cantharidin may be recovered 
unchanged by boiling the cantharidate sol. for a few minutes after acidifi- 
cation w. dil. H,SO,; the cantharidic ac. in the heating loses water and gives 
i. cantharidin, which precipitates out. 





129 


130 GENUS VI, DIV. A. 


(ORDER I, SUBORDER I.) 





ae et ACID ANHYDRIDES AND LACTONES.—Colorless and Solid. 
220 Polyglycolid, (C,H,O,)2—White powder, v. d. s. h. aq.—Reacts neutral, but 


by persistent boiling w. aq. or KOH gives glycollic ac.—Prepare aniline 
derivative, Bl., 30, 102. 


220-1 Camphoric Anhyd.—B. p. 91°.—(Cf. Genus III, A, 2.) 

223-4 Umbelliferone, C,H,O,—(Cf. Genus IV, A).—Odor when warm, fragrant, like 
coumarin. 

334-5 Biphthalyl, C,,H,O,.—Sbl. in ndl.; i. aq.; alm. i. ale. or eth., s. h. glacial acetic 
ac. or conc. H,SO,.—The sol. in conc. H,SO, shows blue fluorescence, but 


becomes transiently emerald-green if a trace of nitric acid is added.—Warmed 
w. KOH sol. gives diphthalylaldehydic ac. 





COLORLESS COMPOUNDS CONTAINING ©, H, AND O [SUBORDER I OF ORDER 1.) 
GENUS VI, ACID ANHYDRIDES AND LACTONES. 


DIVISION B,—LIQUID ACID ANHYDRIDES AND LACTONES WHICH 
DO NOT NEUTRALIZE COLD DECINORMAL SODIUM HYDROX- 
IDE READILY ENOUGH TO TITRATE LIKE SPECIES OF 
GENUS III. 





Oe aaa ACID ANHYDRIDES AND LACTONES.—Colorless and Liquid. 





167 sl.d. | a-Levulinic Anhyd., C,H,O,.—M. p. 18°-18-5°.—E. volatile in air—S. in 21 pt. 
aq. at 15°, but ppt. by K,CO,.—‘‘5 hours’ boiling w. aq. gives levulinic ac.” 

204 $-Methyl-;-butyrolactone, O(.CH,.CHMe.CH,CO.).—G. 1-077°/,—S. in 14-2 pt. 
aq.—BaA, ndl.; v. s. aq.—Pure ac. unknown. 

206c. 7-Butyrolactone, O(.(CH,);.CO.).—G. 1-129'*/,—Misc. w. aq.; separated fr. 
conc. sol. by K,CO,.—Volat. w. st.—Reduces ammon. AgNO,.—‘‘ Boiled 
5 min. w. N/,, NaOH is only 4 converted into salt of acid.’””—Oxid. by 
CrO, to succinic ac. (Test 320). 

206 a-Methyl-;-valerolactone, O(.CHMe.(CH,);.CO.).—S. 20-25 pt. aq.; sat. sol. 
becomes turbid on warming, but clears at 80°.—Acid v. unstable. 

207c. y-Isocaprolactone, O(.CMe,.C,H,.CO.).—M. p. 7°-8°.—G. 1-015'*%?/,—S,. in 
2 pt. c. aq.; sat. sol. becomes turbid on warming, but clears at 80°.—K,CO, 
separates lactone fr. conc. aq. sol.—Free ac. cryst. but unstable, especially 
on warming.—Ag salt ppt. cryst. in flat ndl. fr. h. aq. 

206-9 Coumalin, O(.(CH),.CO.).—G. 1-2001%°/,—Agreeable coumarine-like odor !— 
M. p. +5°.—Misce. w. aq. but separated fr. sol. by K,CO;.—Aq. sol. neutral, 
even after warming.—Neutralizes N/,, NaOH very slowly, giving yellow 
sol.—Neutralized and then boiled w. x’s alkali gives crotonic aldehyde (odor). 

207-S8c. t 7-Valerolactone, O(.(CH,),.CO.).—G. 1-057'8/,—Sapon. Eq. 100.—Misc. w. 
aq.—Ppt’d from the conc. neutral aq. sol. by K,CO,.—Half converted into 
salt of acid after 7 min. boiling w. equivalent quantity N/,,, NaOH; pro- 
tracted boiling w. aq. gives only 6-6% acid.—Ac. very unstable. Its Ag 
salt (AgC,;H,O,), large triclin. ndl. fr. h. aq. 

208-9 $-Levulinic Anhyd., C,H,O,.—G. 1-108(0°).—V. s. aq.—Hydrolyzed v. slowly 
and incompletely by h. aq.—Dec. by c. Ba(OH), sol. to levulinie ac. in 
12 hours. 

215 Valerianic Anhyd., (C,H,O),.0.—G. 0-9297*7/,—‘‘Slowly hydrolyzed by boil- 
ing aq.’’—Vapor produces coughing. When fresh has apple-like odor— 
Sapon. equiv. 93.—Cf. Genus ITI, B, 2. 

215 a-Ethyl-r-butyrolactone, O(.CH,.CH,.CHEt.CO.).—G. 1-035(16°).—S. in 10-11 pt. 
c. <q., sol. becoming cloudy on heating; e. s. alc. or eth.—Separated fr. 
aq. sol. by K,CO,.—Boiling w. alkali gives salt of sirupy soluble ac. 

219-5 a-Ethylvalerolactone, O(.HCMe.CH,.CHEt.CO.).—G. 0-992(16°).—Rather d. s. 
aq.; aq. sol. sat. at 0° becomes turbid at 90°.—Ac. unknown.—Still liq. 


at —i8°. 

220 7-Caprolactone, O(.HCEt.CH,.CH,.CO.).—S. in 5-6 pt. aq. at 0°; K,CO, sepa- 
rates fr. sol—Becomes turbid at 30°-50°, clearing again at 80°.—Still liq. 
at —18°. 

235 (th. i.) | 7-GEnantholactone, O(.HCPr.CH,.CH,.CO.).— V.d.s. aq.— Ac. unknown. — Still 
liq. at —18°. 


254-5 y-Ethyl-0-Caprolactone, O(.HCMe.HCEt.CH,.CH,.CO.).—G. 1 -080°/, —Still liquid 
at —20°.—Misc. alc. or eth.; s. 28 pt. aq.—Feeble aromatic odor.— 
Aq. sol. at first neutral, but a little acid forms after 24 hours in cold w. aq. 
—Ac. unstable liq. 


131 


132 GENUS VI, DIV. B. 


(ORDER I, SUBORDER I.) 





Boiling: point ACID ANHYDRIDES AND LACTONES.—Colorless and Liquid. 


268-71 CEnanthylic Anhyd., (C,H,,0),0.—G. 0-932(21°).—Neutral reaction.—W. cone. 
NH,OH solidifies at once to imide, which recryst. fr. h. aq. melts at 95° — 
Saponification gives acid, b. p. 223°, neut. equiv. 121. 
272 Melilotic Anhyd., o-O(.C,H,.C,H,.CO.).—Odor like sweet grass or Tonka bean! 
—M. p. 25°.—Cf. V, A. 
280-90 Caprylic Anhyd., (C,H,,0),.0.— Odor very disagreeable. — Neutral.—Not at- 
tacked by boiling or distilling w. aq.; though a little acid forms upon long 
exposure to moisture.—Test V gives caprylic ac. (cf. III, B, 2), b. p. 237-5°. 








CHAPTER IX. 
GENUS VII. KETONES 


OF 
SUBORDER I, ORDER I. 
(Colorless Compounds of Carbon, Hydrogen, and Oxygen.) 


THis genus includes all species of the Suborder containing the carbonyl radical that 
have not been described in the earlier genera. These species, with some exceptions, are 
recognized by their behavior towards phenylhydrazine or hydroxylamine in Test VII. 
The few that escape recognition by:this test will at first appear to belong to Genus IX, 
in which they receive mention in connection with a reference to the position in Genus VII 
where they are described. 


GENERIC TEST VII. 


IF THE COMPOUND TO BE EXAMINED IS A SOLID HAVING A MELTING-POINT ABOVE 
30°, EMPLOY PROCEDURE 1 OF THE TEST ONLY. IF IT IS A LIQUID, OR A SOLID 
WITH A MELTING-POINT NOT HIGHER THAN 30°, USE PROCEDURE 2 ONLY. 


PROCEDURE 1. 
(The Test with Hydroxylamine.) 


Fit two dry six-inch test-tubes with perforated rubber stoppers, through each 
of which a meter length of glass gas delivery-tubing 7-8 mm. in internal diameter 
has been inserted. In the first tube place 0.04-0.06 grm. of the powdered sub- 
stance, 0.5 cc. of a hydroxylamine hydrochloride solution,* and 2 ec. of the 
alcoholic sodium hydroxide solution described below. Charge the second tube, 
which is to be used for a blank experiment, in the same manner, except that 0.5 ce. 
of 25 per cent alcohol is to be substituted for the hydroxylamine solution. Support 
both tubes by clamps in vertical positions so that their lower extremities may be 
heated by immersion in the bath represented in Tig. 4 on page 152, which is at a 
temperature of 100°, or in a beaker nearly filled with water already boiling. Allow 
the solutions to boil up briskly for at least five minutes. Then cool; dilute each 
with 10 cc. of cold water, and shake vigorously to precipitate out any substances 
insoluble in dilute aqueous alkali. Filter through double wetted filters, repeating 
if necessary until clear filtrates are obtained. Add one drop of phenolphthalein to 
each filtrate, and then dilute hydrochloric acid, drop by drop, until the red color is 
just discharged. Again close the mouth of each tube and shake vigorously. Note 
whether the solutions remain clear, become turbid or opaque, or give precipitates. 

If the solution from the tube to which hydroxylamine was added gives a pre- 
cipitate, or becomes opaque after neutralization with acid and shaking, while the 

* The Reagents for Test VII (1).—The hydroxylamine hydrochloride solution is made by 
dissolving 7.25 grms. of the purest commercial salt in 9 cc. of water, and diluting to 35 cc. with 
strong alcohol. : i eae 

The soda solution is made by dissolving 10 grms. of the purest sodium hydroxide in 20 cc. 
of hot distilled water, and then diluting to 140 cc. with strong or absolute alcohol. Small 
quantities of both solutions should be kept in stock in laboratories where tests are often made. . 
The hydroxylamine solution may be preserved for some months, at least, without seriously 


deteriorating in strength. The soda solution will soon become strongly colored on keeping 
unless it is prepared with unusually pure alcohol. jes 


134 KETONES 


solution in the blank experiment remains clear, or only becomes opalescent or slightly 
turbid, the compound under examination is to be sought in the tables of Genus VII. 
The precipitate in this case consists of an oxime which is soluble in alkali, but not 
in a neutral aqueous solution. A majority of the oximes which are precipitated 
in this test—though there are many exceptions to the rule—dissolve in an excess 
of cold dilute hydrochloric acid to clear solutions, from which they may be again 
precipitated by neutralization and shaking. 


PROCEDURE 2. 
(The Test with Phenylhydrazine.) 

If the unknown compound is readily soluble in water, dissolve one drop in 
2 cc. of cold water in a dry six-inch test-tube 18-20 mm. in diameter, and add four 
drops of a phenylhydrazine solution prepared by the method described below.* 
If the compound is not soluble in water, substitute for the latter 2 cc. of dilute alcohol 
(one volume of strong alcohol to two volumes of water). It is not necessary 
in this case that the substance should dissolve visibly. Suspending the test-tube 
by its lip between the thumb and forefinger, sway it from side to side with a slow 
pendulum motion (one or two swings a second) for at least a minute. Vigorous 
shaking might spoil the test by breaking up a difficultly soluble substance into 
minute droplets and forming an opaque emulsion. ) 

If the solution remains clear, stopper the tube very loosely with a clean cork, 
and stand it upright in a beaker containing a layer of water 2-3 cm. deep. Have 
the water gently boiling at the moment when the tube is introduced, and continue 
to heat at 100° for five minutes. The water in the beaker should not boil actively 
during this period, for the steam arising then heats the side walls of the test-tube 
to such an extent that the loss of alcohol by evaporation may become too impor- 
tant a factor in the final result, and violent bumping of the mixture may cause emul- 
sification of the original mixture. Whenever this test in hot solution has to be 
applied, a blank experiment must be made at the same time, using the same quan- 
tities of the substance and solvent, but omitting the phenylhydrazine. 

If the solution still remains clear after five minutes’ heating, remove it from 
the water-bath, and, after allowing it to stand twenty-five to thirty seconds, care- 
fully observe its degree of transparency and its color. (The delay in making this 
observation is mainly to permit suspended drops of unchanged substance to settle 
out. The appearance of a precipitate or opacity after thirty seconds may be caused 
by the separation of the original substance from its supersaturated solution, and is 
without significance.) To test for opacity, hold the test-tube in front of, and in 
actual contact with, a piece of white paper on which a small cross has been drawn 
in lines 1 mm. in width in black ink. If the cross can not be seen through the 
solution when the position of the test-tube is slightly changed, the solution is to be 
considered ‘‘opaque.”’ 

* (The Phenylhydrazine Reagent for Test VII (2).—Mix 0.3 cc. of glacial acetic acid with 
7.0 ec. of cold water. To the mixture add 2 cc. of light-colored phenylhydrazine. The clear solu- 
tion, if not exposed to direct sunlight, will remain in good condition for four or five days, but then 
becomes strongly colored and should be thrown away. If the phenylhydrazine does not give a 
clear solution in the specified mixture of acetic acid and water, it must be redistilled, and the end 
fractions of the distillate rejected. Phenylhydrazine often undergoes slight decomposition in 


storage, and the products—of which benzene is one—then interfere with the preparation of the 
reagent by causing a separation of layers.] 


KETONES. 135 


Any compound to whith Test VII-2 has been applied is probably a ketone: 

(a) If an ‘‘opaque” solution is obtained on treating it with phenylhydrazine 
in, the cold by the method of the first paragraph. 

(b) If an ‘“‘opaque” solution is obtained during the five minutes’ heating 
described in the second paragraph, or within thirty seconds after its removal from 
the bath, provided the solution in the corresponding blank experiment remains 
clear, or nearly so. 

(c) If both solutions mentioned in (b) become ‘‘opaque” after heating, but 
the solution of the blank test remains unchanged in color, while the suspended 
matter in the solution containing phenylhydrazine assumes a much deeper yellow 
color. 

Observations on Generic Test VII. 

In using Procedure 2 of this test the analyst should never lose sight of the 
danger that exists of mistaking an alcohol or hydrocarbon containing traces of 
aldehydic impurities for a ketone; for aldehydes yield insoluble phenylhydrazones, 
and give opaque solutions under the test conditions, quite as easily and uniformly 
as the species of Genus VII. 

A contamination with aldehyde that is barely sufficient to produce a very faint 
pink ‘coloration with the fuchsine reagent in Test I, may cause a pronounced tur- 
bidity in the test with phenylhydrazine. Conclusions as to the ketonic character 
of a substance of doubtful homogeneity which reacts slightly with the fuchsine 
reagent, can not, therefore, be safely drawn from Test VII-2. It is necessary 
that such bodies shall first be purified with every possible care. 

Of the two procedures 1 and 2, neither one can be trusted for the recognition 
of ketones belonging to the group for which its alternative is prescribed in the 
‘“generic test;”? though it is true that most solid species do show a ketonic behavior 
in Procedure 2, and that very many liquid ketones, which it is directed shall be 
examined by Procedure 2, would also react as ketones when tested by Procedure 1. 

Both reactions, in the form recommended, fail in certain special cases. Thus 
they are not given by aromatic ketones having two alkyl radicals substituting in 
the ortho position to the carbonyl group; or by the fatty ketones (C,H,,+,),CO., 
in which ‘“‘n”’ is 9 or a higher number, though still given by caprone (C;H,,),CO.* 
The liquid aliphatic ketones which are soluble in water are, in general, readily rec- 
ognized by Procedure 2, but not by Procedure 1. 

In explanation of the numerous rather arbitrary conditions imposed in these 
procedures, it should be said that the tests as they stand are the result of informa- 
tion obtained from a study of the behavior of about one hundred purified and typical 
species of Genera VII, VIII, and LX towards hydroxylamine and phenylhydrazine 
under a great variety of carefully controlled conditions. By lengthening the period 
of heating with the reagents, and by other devices, the number of ketones calling 
for mention in the tables of Genus IX might have been somewhat reduced, and a 
slight gain made in the direction of simplicity of classification; but this advantage 
would have been more than offset by the increased length or experimental difficulty 
of the operations necessitated. 

* The oximes of the higher fatty ketones are formed in the test with hydroxylamine, but 


they are not soluble enough in alkali to give a precipitate or opaque solution in the neutraliza- 
tion with acid. 


COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I] 


GENUS VII, KETONES. 


DIVISION A,—SOLID KETONES. 





Melting-point 
COE): 


20-5 


26-6°-5 


27 


27 
28 


28 
30 
30 


33-9 
33-4 


36 


38 
39 
39 
40 


40 


41-2 


42 


42-3 


Boiling-point 
CO): 


202 


306 


215 


273-5 


198-5 


263 


264c. 


330: 6c. 


205-6(100 mm.) 


318c. 


196 
294 
229d. 
178 


244 


260-2 (th. i.) 


KETONES.—Colorless and Solid. 


+ Acetophenone, Me.CO.Ph.—Odor aromatic!—Alm. i. aq.— 
(When melted, often refuses to solidify unless a crystal is 
added.)—Sol. in Test VII-2 becomes opaque and gives 
yellowish-white ppt. after 30 seconds in the cold. Color- 
reaction 701 is quite characteristic.—Identify by Test 712! 

Allotropic Benzophez:one, C,,H,,0(?).—Eth. sol. on evapo- 
ration leaves an oil that solidifies to benzophenone (m. p. 
48°-9°) upon contact w. a crystal of the latter substance. 

Methyl Benzyl Ketone, Me.CO.CH..Ph.—Combines easily w. 
NaHSO,.—Mixed w. phenylhydrazine, reacts at once w. 
evolution of heat and separation of aq., giving a hydra- 
zone, lft. fr. lgr., m. p. 83°. 

p-Propionylanisol, Et.CO.C,H,.OMe.—KMn0O, oxid. to anisic ac. 
—M. p. of oxime, 67°. 

t Phoron, C,H,,0.—Slightly yellow cryst.—Adds Br, in- 
stantly in the cold in CS, sol.; the addition product cryst. 
fricalew toe Oo. 88°-9°.—Sol. in Test VII-2 becomes 
opaque and yellow after 3 min. heating. 

Methyl Undecyl Ketone, Me.CO.C,,H,,.—G. 0-829 (28°). 

p-Propionylphenetol, Et.CO.C,H,.OEt.—Oxime, m. p. 97°. 

Dihexyl Ketone, (C,H,;),.CO.—G. 0.825 (30°).—V. s. ale. or 
eth. 

Dibenzyl Ketone, (C Hy)». CO.—Test 702 gives benzoic ac.— 
M. p. oxime, 119-5°. 

Tetradecanone(2), Me.CO.C,,H,,.—Test 702 gives lauric and 
acetic ac. 

Phenyl p-Xylyl Ketone, Ph.CO.C,H,.Me,.—V. s. ale. or eth.— 
Stable towards oxid. agents. Warming w. conc. H,SO, 
splits off benzoic ac. (Test 312.) 

Camphenylon, C,H,,:CO.—Strong camphor odor. Shoes 
oxime, ndl. fr. “eth., m. p. 105°-6°. 

Methyl Tridecyl Ketone! Me.CO.C,,H,,,—G. 0-818 (39°). Gives 
an oxime, 

Furfuralacetone, C,H,O.CH:CH.CO.Me.—Sol. in acetylchlo- 
ride is light red, becoming emerald-green on warming. 
Diheptyl Ketone, (C,H,,),.CO.—Ndl. fr. ale—Probably does 
not give a very satisfactory ketone reaction in Test VIJ-1. 

a-Hydrindone, C,H,0.—Rhombic tbl. v. s. ale.—Oxid. by 
Test 905-3, gives phthalic ac. (Test 318-1)—M. p. of 
oxime 146°. 

Benzalacetone, Me.CO.CH:CH.Ph.—Thick tbl. e. s. alc. or 
eth.—S. in conc. H,SO, w. orange color.—Dibromide melis 
atr.l247-57% —Oxime: melts at 115°—Forms NaHSO, comp. 
easily. 

Vinyl Phenyl Ketone, C,H;.CO.Ph.—Ndl. v. s. ale. or eth.— 
NaHSO, comp. forms slowly. 


p-Tolyl Hexyl Ketone, C,H,.CO.C,H,,.—Oxime is an oil. 





136 


GENUS VII, DIV. A. 137 


(ORDER I, SUBORDER I.) 











oe ta aaa as as KETONES.—Colorless and Solid. 
43-3°5 230-1 Hexadecanone(2), Me.CO.C,,H.».—Test 702 gives myristic and 
acetic acids. 
46 310c. Diacetylmesitylene, Me,.C,H.(CO.Me),.—Pr. fr. lgr. 
48 319-20 Methyl Quindecyl Ketone, Me.CO.C,,H;,. 
48-8 -5 306c. t+ Benzophenone, Ph,.CO.—Rhombice pr., i. aq.; e.s. ale. or eth. 


—Sodium gives an intensely dark blue compound when 
gently heated w. the fused ketone! Identify by Test 714! 
50-1 323 Propyl Naphthyl Ketone, Pr.CO.C,,H;.—S. ale.—Oxime m. p. 
89°.—M. p. picrate 68°-9°. 
51-2 251-2(100 mm.)| Octadecanone(2), C,,H,;.CO.Me.—Gives oxime. 


51-2 300-1 $-Methyl Naphthyl Ketone, Me.CO.C,,H;,—Ndl. fr. Igr.— 
nce m. p. 142°-3°.—Dibrom.-derivative, fr. CS,, m. p. 
abt. 56 266 (110 mm.) | Methyl Heptadecyl Ketone, Me.CO.C,,H,,.—Gives oxime. 
57 Benzyl Naphthyl Ketone, C,H,.CO.C,,H,—Tbl. fr. alc., e. 9. 
alc. or eth, 
57-8 345-8 {+ Benzylideneacetophenone, Ph.CH:CH.CO.Ph.—Pale yellow- 


ish rhombic pr., s. alc., e. s. eth——Gives isomeric solid 
oximes.—Heated w. HCl (sp. gr. 1-12) at 200° gives benz- 
_ aldehyde and acetophenone. 

58 4.350 + Dinonyl Ketone, (C,H,,),.CO.— Pearly lft. fr. ale-—{This, 
and the other symmetrical aliphatic ketones higher in 
the series, do not give Test VII-1 satisfactorily, because 
their oximes are not readily soluble in alkali.] 


59 m-Methylhydrindone, C,,H,,0.—Long ndl. fr. lgr. 
59 251 (15 mm.) | Phenyl Pentadecyl Ketone, C,,H,,0.—V. d. s. c. alc.; s. eth. 
59-60 326 (th. 1.) { p-Phenyl Tolyl Ketone, Ph.CO.C,H,.—(M. p. cf dimorphous 


hexagonal form is 55°.)—S. c. alc.; e. s. eth.—Oxid. by 
CrO, mixture to p-benzoyl-benzoic ac.—Gives isomeric 
solid oximes, m. p. 153°-4° and 115°-6°.—Heated w. 
soda-lime at 300° gives benzene (Test 913), and p-toluic ac. 

60 262 (15 mm.) | p-Tolyl Pentadecyl Ketone, C,,H,,0. 

60 320-2c. Desoxybenzoin, Ph.CO.CH,.Ph.—Tbl. d. s. h. aq.; e. s. ¢. alc. 
or eth.—Easily attacked by HNO, or bz.—Oxime, ndl. fr. 
ales Me DAvS. 

61 220-5d. $-Hydrindone, C,H,O.—E. s. alc. or eth.—Oxime, ndl. fr. 
dil. alc., m. p. 155°.—M. p. of phenylhydrazone 120°.— 
Oxid. by KMnO, gives homophthalic ac. 

63 2, 5-Dimethyl-3, 4-diacetylfurfuran, C,,H,,0,—Fine silky ndl. 
fr, h. aq., w. peculiar faint aromatic odor when warmed.— 
S. in cone. H,SO, and ppt’d unchanged by aq. 


63 p-Methylhydrindone, C,,H,,0.—Ndl. fr. lgr., e. s. alc. or eth. 

67 278 (15 mm.) | p-Tolyl Heptadecyl Ketone, C,H,.CO.C,,H;,.—V. d. s. c. ale. 
—Oxid. by Test 905-3 gives p-toluic ac. 

68 dec. Methyl Cinnamenylvinyl Ketone, C,,H::0.—Rhombie plates 


fr. eth.; e. s. alc. Color soon changes to light yellow.— 
Oxime, m. p. 153°.—Adds Br, easily in ethereal sol., giving 
dibromide of m. p. 173-5°. 


69 Laurone, (C,,H.;)..CO.—I. c. ale——Probably does not give 
Test VII-1, oxime not being sol. in alkali. 
72-3 a.360 Benzylacetophenone, C;H,;.CH,.CO.Ph.—V.s. alc. or eth.—Oxid. 


by Test 905-1 gives benzoic ac. (Test 312).—Br substitutes 
easily.—Oxime, m. p. 87°, v. s. ale. 
73 255-60 Methyl s-Duryl Ketone, Me,.C,H.CO.Me.—Pearly lft. 
75-5 385 a-Phenyl Naphthyl Ketone, Ph.CO.C,)H;.—S. 41 pt. alc. at 12°.— 
Heating w. soda-lime at 350° gives naphthalene (Test 915) 
and benzoic ac.—Oxime, m. p. 140°-2°. 


138 





Melting-point 
(C.°). 





76°3 


78 


81-5-2-5 
82 


82-8 


83 
83-5—-4 
85 


85-5-86 


87-8 


92 


93-4 
94 


95 
95 


99 
99- 5-100 


102-3 
104-5 


106 
107-10 


109-10 
112-2-5 
115 


117 


GENUS VII, DIV. A. 


(ORDER I, SUBORDER I.) 





KETONES.—Colorless and Solid. 





t Myristone, (C,;H,7;),.CO.—Scales fr. abs. ale.—Oxime being v. 
d. s. in alkali does not give Test VII-1. 

6-Phenylindanone(7), C,,H,,0.—B. p. 344° d.—E, s, alc. or eth. 
—Reduces ammon. AgNO; sol. on warming.—Oxime, m. p. 
141°.—Oxid. by Test 905-3 gives benzoic and phthalic ac. 
(Tests 312 and 318-1). 


Lactarone, (C,,H.,)..CO.—Pearly lft. fr. ele. 

f-Phenyl Naphthyl Ketone, Ph.CO.C,,H,—Ndl. s. 49 pt. ¢. alc. 
—Picrate fr. sat. sol. of picric ac. in bz., m. p. 112°-13°.— 
Heating w. soda-lime gives naphthalene (Test 915) and ben- 
zoic ac. (Test 312). 

Palmitone, (C,,H,,),.CO.—Lft. fr. ale—Oxime heing v.d. s. alk., 
probably does not give Test VII-1.—Gives no NaHSO, 
comp. 

Isodiphenylene Ketone, C,,H,O.—D. s. ale.—Stable toward oxid. 
agents.—Not changed by fusion w. KOH. 

Diphenylene Ketone, (C,H,),.CO.—Large yellow tbl.—See Sub- 
order IT. 

Methyl Pentamethylphenyl Ketone, C,,H,,0.—E. s. alc. or eth._—~ 
Oxid. by c. KMn0O,. 

Oxyacetophenone, Ph.CO.CH,OH.—-V. s. alc. or eth.; s. h. aq.— 
Decomposed by heat alone, or by heating w. NaOH, giving 
benzaldehyde (Test 113).—Reduces Tollen’s reagent giving 
benzaldehyde.—Gives Test 702. 

+ Stearone, (C,,H,,)..CO. — Lft. d.s. h. ale. or eth. — Dibrom- 
derivative, m. p. 72°.—Because of insolubility of oxime 
in alkali does not give Test VII-1. 

s-(p)-Dimethylbenzophenone, (C,H,.Me),.CO.—B. p. 335°-7°.— 
V.s. alc. or eth_— HNO, (sp. gr. 1-51) gives dinitro-comp., 
s. bz.; m. p. 144°.—Oxime, pr. fr. alc., m. p. 163°.—Boiled 
w. solid KOH gives p-toluic ac. 

9, 9-Dimethyldihydroanthrenone(10), C,,H,,O.—Cryst. e. s. eth. 
or bz.—Oxid. by CrO, to acetic ac. and anthraquinone. 

Phenyl-p-Xylyl Ketone, Pb.CO.CH,.C,H,.Me.—4-sided pr.— 
Oxime, m. p. 108°. 

Benzoinethylether, Ph.CH(OEt).CO.Ph.—Pr. e. s. alc. or eth. 

o-Methylhydrindone, C,,H,,0.—Ndl. fr. lgr—Oxid. by Test 
905-3 to methyl-phthalic ac. 

Benzoylveratol, (MeO),.C,H;.CO.Ph.—Ndl. fr. alc. 

m-Phenylene Diphenyl Ketone, C,H,.(CO.Ph),.—Dist. undec.— 
Oxime, m. p. 201°.—Fusion w. KOH gives only benzoic ac. 
(Test 312). 

Cinnamyleneacetophenone, C,,H,,0.—Cf. Suborder II. 

Ledum Camphor, C,,H,,O (fr. leaves of Ledum palustre, wild 
rosemary).—Sbl, v. e. in long ndl.—Sol. in cone. H,SO, be- 
comes violet w. a drop of HNO,.—Gentle heating w. 50% 
H,SO, gives a sesquiterpene, b. p. 255°. 

Cinnamylenebenzylideneacetone, C,,H,,0.—Cf. Suborder II. 

$-Dibenzoylacetone, C,,H,,0;.—Ndl., d. s. eth., CHCl, and lgr.; 
s. in 100 pt. bz.—(Alcoholic sol. gives no color w. FeCl,.) 

Anisoin, C,,H,,0,.—Ndl. d. s. c. ale. or eth.—S. in cone, H,SO, 
w. pale-green color changing to yellow and purple-red on 
warming !—Reduces Fehling’s sol. 

t Dibenzylideneacetone, (Ph.CH:CH),.CO.—See Suborder IT, 

Methylhydrocotoine, (MeO),.C,H,.CO.Ph.—Br  substitutes.— 
Fusion w. KOH gives benzoic ac., etc. é 

Dibenzoylmesitylene, (Ph.CO),.C,H.Me;.—B. p. abt. 300°. 





GENUS VII, DIV. A. 139 


(ORDER I, SUBORDER I.) 
A ESS, 








cag rout oe Sate KETONES.—Colorless and Solid. 
Ce ere eg a eee ee eee eae Ge TN 
119-20 DL ke aan (Ph.CO),.CH.Ph.—B. p. 300°5° (15 
mm.). 
120 Piperonyloine, C,,H,,0,.—Oxid. by dil. HNO, (Test 905-3) gives 
oxalic ac. (Test 317). 
121 m-Acetylbiphenyl, Me.CO.C,H,.Ph.—B. p. 325°-7°.—E. s. alc. 
or acetone.—Oxid. by CrO; in Ac. to m-phenylbenzoi. ac. 
121c. Acenaphthenone, C,,H,O.—Ndl. v. s. ale.—Gives substitution 


product w. Br in CS, sol., m. p. 112°.—Boiled w. Zn dust and 
are 4c gives acenaphthylene.—Oxime, Ift. fr. alc., m. p. 
175°. 

126 1, 2, 4-Triphenylbutanedione(r1, 4), Ph.CO.CH(Ph).CH.,.CO. Ph.— 
Upon sol. in ¢. cone. H,SO, and addition of aq. gives ppt. of 
triphenylfurfurane —Oxime, m. p. 151°. 


129 I, 2, 4-Triphenylbutenedione(1, 4), Ph.CO.C(Ph):CH.CO.Ph.— 
Yellowish ndl., v. d. s. ale. or eth—Dry, adds re cold: 
moist, Br substitutes. i 

abt. 133 } Benzoin, Ph.CH(OH).CO.Ph.—B. p. 343°-4°.—6-sided pr. 
(often pale sulphur-yellow).—I. ¢. aq.; v. d.s. h.aq.; s. h. 
alc.—Gives Test VIJ-1.—Ale. sol. reduces Tollen’s reagent 
(Test 101) !—Strongly heated above b. p. gives faint odor of 
benzaldehyde.—Boiled w. normal NaOH sol. in porcelain 
dish while air is blown through the solution the liquid soon 
assumes a RVT1 ated ean Test 713. 

135 - af-Dinaphthyl Ketone, (C,)H;),.CO.—S. in 77 pt. alc. at 14°; 
e. s. eth.—Heated w. soda-lime at 350° gives naphthalene 
and a- and f-naphthoic ac. 

144-5 Diphenylbutanedione(1, 4), Ph.CO.CH,.CH,.CO.Ph.—Ndl. d. s. 
ale. or eth.—Sol. in conc. H,SO, is green, becoming red- . 
brown w. blue-green fluorescence on warming.—Dioxime, 
m. p. 203°-4°. 

159 s(-p)-Ditoluylethane, C,H,.CO.CH,.CH,.CO.C,H,.—NdLl., v. d.s. 
c. alc.; e. s. bz.—Boiling w. ammonium acetate and glacial 
Ac gives p-ditolylpyrrol. 


159-60 Terephthalophenone, C,H,.(CO.Ph),..—Ndl. or lft., d. s. c. ale. or 
eth.—Oxime, m. p. 212°-13°; dioxime, fr. dil. alc., m. p. 235°. 

162-3 Triacetylbenzene, C,H;.(CO.Me),.—Small ndl. d. s. aq., alc., or 
eth.—Oxid. by HNO, gives trimesic ac. 

17355 Diacetyldibenzylethane, C,)H,,0,——Ndl. fr. ale.—I. aq. or dil. 
alkalies. 

176-4 +[+]Camphor, C,H,,0. — (‘‘Camphor.”’) — B. p. 205-3°. — 


Tough, white cryst., translucent, slightly unctuous mass, w. 
peculiar, penetrating, fragrant odor, and bitter, pungent 
taste! Small fragments thrown upon pure water, float and 
assume singular circulatory movements, which immediately 
cease upon the addition of a drop of oil_—Very volatile, sub- 
liming crystalline on sides of vessels in which it is contained 
at ordinary temperatures, and in the saponification test soon 
passing out of flask and depositing in condenser !—V. d. s. 
aq.; v. s. ale; e. s. eth.—Identify by Test 715! (The 
oxime forms so slowly that camphor does not give an appre- 
ciable ppt. in Test VII—1.)—‘‘ Synthetic Camphor ”’ is opt. 1. 

198 + a-Dibenzaltriacetophenone, C,,H,;,0;.—Cryst. fr. bz.; v. d.s. 
ale.—Ppt. in Test VII-1 rather scanty.—Dist. splits to 
acetophenone (Test 712) and diphenylpropenone.— Warmed 
w. alc. NaOH gives () isomer, m., p. 256°. 

208 . Phenyloxanthranol, C.)H,,0,—Rhombic tbl., i. alkalies; e. s. 
alc.; s. conc. H,SO, w. intense purple-red color.—Warmed 
w. glacial Ac and Zn dust gives phenylanthranol. 


232 ‘¢ Octahedral’? Oxylepidine, C,,H,,0,.—Cf. Suborder IT. 


Eee 
———— ee 


140 | GENUS VII, DIV. A. 


(ORDER 1, SUBORDER I.) 


nese oe eat KETONES.—Colorless and Solid. 





————$—$—$———$ 


256) as . + (6)-Dibenzaltriacetophenone, C,.H,.0,.—Thin lustrous" 





269-70 Duryldibenzoyl, Me,.C,.(CO.Ph),.—Small pr. s. bz.; alm. i. b 
ale.—Sbl.—Fusion w. KOH gives benzoic ac. and durene. 


289 Truxone, (C,H,O) z.—Sbl. in ndl.—Cryst. fr. HNO, (sp. gr. 1-3 
in long lustrous ndl. ‘a 


ot se 
= 
” 
: Ky 
1 co h/ ie 
‘ » AT 
oil ye ce = Hin. aha ail 
oa 
we 
ry » oy 
ta 
Pe 
Spat eee 
s . ri, * 
2 ie) 
hs fesse oe 
: 4 Py rae 
y ml mat no 
, 7 > dl i a ‘ 
~ f ir Weer Bi gg 


COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER J]. 
GENUS VII, KETONES. 


Boiling-point 
CORE 


56- 5c. 
80-6 
87-5-8 
95 


98-102 
102c. 


102 -7c. 
106 (th. 1.) 


114 
114-5 
116 
118c. 


122 
122-4 


123-7 
126 
127 
128 


128-30 


129-5-30c. 


130c. 


132 


DIVISION B,—LIQUID KETONES. 


Specific . 
Gravity. 


0-819°/, 
0-805(19-8) 
0-973(22) 


0-822°/, 


0-812(15) 
0-834°/, 


0-800(16) 


0-830°/, 
0 ef 80217 /, 
OFS18'**/, 


0-861(15) 
0-818(17-5) 


0-8067°/, 

0-810(21) 

0-830(0) 
0-920(21-7) 
0-834?"/,7.5 


0-85829/, 


0-9427-5/, 


0-825(21) 


KETONES.—Colorless and Liquid. 


t Acetone, Me.CO.Me.—Misc. w. aq., alc., or eth.—Odor alco- 


holic-ethereal.—Identify by Test 711! 

{ Methyl Ethyl Ketone, Me.CO.Et.—Odor like acetone.—Oxid, 
by Test 702 gives acetic ac. only! . 

} Diacetyl, Me.CO.CO.Me.—Yellow liquid w. peculiar sweetish- 
pungent odor. (Belongs to Div. B of Suborder IT.) 

Methyl Isopropyl Ketone, Me.CO.Pr.—Oxid. by Test 702 gives 
Ac and COQ,. 

2-Methylbutenon(1, 3), Me.CO.CMe:CH,. 

t Methyl Propyl Ketone, Me.CO.Pr.—Test 702 gives acetic and 
propionic acids. 

t Diethyl Ketone, Et.CO.Et.—CrO, oxid. to acetic and propionic 
acids (cf. Test 702).—Gives NaHSO, comp. w. difficulty. 

+ Pinacoline, Me.CO.C.Me,.—Alm. i. ag.—Peppermint-like odor. 
—No NaHSO, comp.—Test 702 oxid. to trimethylacetic ac. 
—Treated w. Cl cold gives C,H,,Cl,0, m. p. 51°; b. p. 178°.— 
Becomes opaque and yellow in 10 sec., cold, in Test VII-2. 

Acetyltrimethylene, Me.CO.C,;H,;. — Polymerized by mineral 
acids.—_KMn0O, gives trimethylenecarbonic ac. 

Ethyl Isopropyl Ketone, Et.CO.Pr. . 

Methyl Isobutyl Ketone, Me.CO. Bu.—Strong camphor-like odor. 
—Test 702 oxid. to isobutyric, isovalerianic, and acetic acids 
(disagreeable odor).—Gives a NaHSO, comp. 

Methylethylacetone, Me.CO.CH(Me)Et.—Peppermint-like odor. 
—Test 702 gives acetic ac. (Test 311). 

Ethylideneacetone, Me.CH: CH.CO.Me.—S. aq. 

Ethyl Propyl Ketone, Et.CO.Pr.—Test 702 oxid. to Ac, pro- 
pionic and butyric acids. 

Diiosopropyl Ketone, (Me,.CH),.CO.—No comp. w. NaHSO;.— 
CrO, gives acetic and isobutyric acids (Test 702). 

2, 2-Dimethylpentanone(3), Et.CO.C.Me,.— Camphor odor. — 
Test 702 gives Ac and trimethylacetic ac. 

Methyl Butyl Ketone, Me.CO. Bu. 

Acetylcarbinolethylether, Me.CO.CH,.OEt.—Misc. w. aq.—Rc- 
duces Tollen’s AgNO, reagent —In HCl sol. gives acetore 
and ethyl alc. w. Na amalgam. 

Allylacetone, Me.CO.(CH,),.CH:CH,.— Unpleasant odor.—Test 
702 oxid. to acetic and oxalic ac. (Tests 311 and 317). 

+ Mesityl Oxide, Me,.C: CH.CO.Me.—Peppermint odor.—I. aq. ; 
v. s. ale.—Boiled w. v. dil. H.SO, yields acetone (Test 711). 
—Gives no NaHSO, comp.—Shaken w. phenylhydrazine re- 
acts w. evolution of heat (product oily). Solution opaque 
and yellow in 5 sec. in cold, in Test VIJ-2. 

Cyclopentanone, C,H,CO.—Peppermint odor —Dil. HNO, gives 
glutaric and succinic ac.—Semicarbazon, m. p. 200°-5° d. 

3, 3-Dimethylpentanone(2), Me.CO.C(Me,)Et.—Test 702 oxid. to 
dimethylethylacetic ac. 








141 


142 


GENUS VII, DIV. B. 


(ORDER I, SUBORDER I.) 





Boiling-point 
(CS): 





135 
136 


135-40 
137 -5-9 
141-3 
144c. 


144 


147d. 


149-50 
151 
151-2 


155 
155-6 
155 


163-5-4-5 


169 
170 
170-1 
172-5 


173-4 
173-4 
174-5 
176-7 


179-81c. 
180 
181-2 


190 
192-3 


194 (th. i.) 


196-8 
202 (th. i.) 


oe) Kay (=: 


i 


io) 


ry 


Specific 
Gravity. 


-907(15) 
-815!7/, 
-815(20) 
-817(22) 
-91429/, 
-818 (17-2) 


-914(0) 
-829(21) 
-837(0) 


-831(0) 
.900(15) 
-94770/, 
-931(25) 
-909(20) 
-850(0) 


-817(19) 
-819?°/, 


-860(20) 


-000(15) 
-969(0) 

-827(16) 
-833(20) 


-82520/, 
-947(19) 


-97020-8/, 


-032(15) 


KETONES.—Colorless and Liquid. 





Methyl Tetramethylene Ketone, Me.CO.C,H,.— Peppermint odor. 
—Gives a NaHSO, comp. 


Ethyl Isobutyl Ketone, Et.CO. Buu—Test 702 oxid. to acetic and 
isovalerianic ac. 

2, 3-Dimethylpentanone(4), Me.CO.CHMe.CHMe.. 

3-Ethylpentanone(4), Me.CO.CHEt,.—Gives a bisulphite comp. 

1-Methylcyclopentanone(3), Me.C,H;,.CO.—Opt. active [+]. 

Methyl Isoamyl Ketone, Me.CO.C,H,,.—Test 702 oxid. to 
acetic, isovalerianic and isocaproic ac. 

Dipropyl Ketone, Pr.CO.Pr.—I. aq.—Test 702 oxid. to pro- 
pionic and butyric acids.—Gives no NaHSO, comp. 

Acetylcarbinol (Acetol), Me.CO.CH,OH.—Misc. w aq., alc., 
or eth.—‘‘Faint, sickly odor’ !—Reduces Fehling’s sol. 
cold.—Combines w. 2 mols. phenylhydrazine at 100° 
forming methylglyoxalosazone, m. p. 145°.—Phenyl- 
hydrazone oily.—‘‘Soon acquires acid reaction.” Posi- 
tion in tables in -doubt. 

2-Hexinone(5), Me.CO.CH,.C : C.Me. 

3, 3-Dimethylhexanone(4), Et.CO.C.(Me.,) Et. 

Methyl Amyl Ketone, Me.CO.C,H,,.—Oxid. by Test 702 to 
acetic and valerianic acids.—Gives a NaHSO, comp. 

Propyl Isobutyl Ketone, Pr.CO. Bu.—Gives no NaHSO, comp. 

Propionylcyclobutane, Et.CO.C,H, Gives a NaHSO,; comp. 

Cyclohexanone, (CH,),:CO.—Odor like acetone.—EH. s. aq.— 
Dil. HNO, oxid. to adipic ac.—Gives comp. w. NaHSQO,. 

Diacetone Alc., Me.CO.CH,.CMe,.OH.—Misc. w. aq. or ale.— 
Sol. in conc. H,SO, gives mesityl oxide. 

[+ ]-1-Methylcyclohexanone(3), Me.C,H,0. 

Ethyl Amyl Ketone, Et.CO.C,H,,.—-Gives no comp. w. NaHSO,. 

2-Methylheptanone(6), Me.CO.(CH,),.CHMe,. 

Methyl Hexyl Ketone, Me.CO.C,H,,.—Oxid. by HNO, gives 
cenanthic and acetic acids.—Gives comp. w. NaHSO,. 

Dipropylacetone, Pr..CH.CO.Me. 

2-Methylheptene(2)-one(6), C;H,,-CO.—KMnO, oxid. to ace- 
tone and levulinic ac.—Gives purple-red color to pine 
splinter moistened w. HCL. 

as.-Diallylacetone, (C,H,),.CH.CO.Me. 

Hydracetylacetone, Me.CH(OH).CH,.CO.Me.—S. aq., alc., eth., 
or CHCl,.—Gives phenylhydrazone, m. p. 85°-7°. 

Suberone, C,H,,:CO.—Peppermint odor.—Adds Br easily. 

Methylbutyroue, C,H,,0.—Conc. HNO, oxid. to cenanthie ac. 

2, 6-Dimethylheptanone(4), (Me,.CH.CH,),.CO.—NaHSO, gives 
no comp. 

Ethyl Hexyl Ketone, Et.CO.C,H,,.—Solid at —8°. 

}+[+]}Fenchone, C,,H,,O (from oil of fennel.)\—Odor pleas- 
ant and camphorous!—M. p. +5°-6°.—Heated w. P.O, 
gives m-isocymene.—S. without decomposition in cone. 
H,SO,.—Gives an oxime, m. p. 164°-5° (x. h.). 

t Acetonylacetone, Me.CO.(CH,),.CO.Me.—K. s. aq., alc., or 
eth.—Gives pyrrol test (Test 703) w. splinter.—Combines 
w. x’s phenylhydrazine on warming to osazone, cryst. 
fr dil. alc., m. p. 120°. ; 

4-Methyloctonone(2), C,,H,,0. 

+ Acetophenone, Me.CO.Ph.—Alm. i. aq.—M. p. 20.5°.—Gives 
Test VII-2 readily in the cold.—Identify by Test 712! 





GENUS VII, DIV. B. 143 


(ORDER I, SUBORDER I.) 


eee ences erences eee ri icc 


Boiling-point 
(C,?). 
200-5 


203 


204-5 
200-10 © 


206c. 


206-7 
206-8 
207 


208-9d 


211 
210-15 


215 
217 


218 


220-2 
221-2 
221-2 


222 


224 
223-6 
224-5 


224-5 


O- 


Specific 
Gravity. 


939(12) 


-913(20) 


-841(17) 


-913(0) 


8242057, 
-900(20) 
-896(20) 


-016(0) 
-825(20) 


-948?9/, 


-010(3) 


-009(0) 


-932(20) 


-928(19) 


1-013 


-829(17-5) 


-998(17-5) 


-996(19) 


-989(20) 


KETONES.—Colorless and Liquid. 





Camphorphoron, Me,C:C,;H,O.Me.— Odor spicy. — Tribrom- 
comp., m. p. 52°. 


{ Thujone (Tanacetone), C,,H,,O (fr. tansy-oil, Tanacetum 
vulgare).—Odor somewhat like tansy.—Opt. active [+]. 
—(NaHSO, comp. i. eth., forms very slowly.)—Dist. fr. 
P.O, gives cymene —Boiling w. FeCl, gives carvacrol.— 
a-oxime, m. p. 54-5°——5 cc. Br+5 grms. thujone and 
30 ce. Igr. (cold) gives tribrom-deriv., d.s. alc., m. p. 121°-2°. 

Ditetramethylene Ketone, (C,H,)..CO.— Peppermint odor. — 
NaHSO, comp. e. s.—Combines w. phenylhydrazine. 

Isopropyl Hexyl Ketone, Me,.CH.CO.C,H,;.—Gives no NaHSO, 
comp. 

a-Menthone, C,,H,,0.—Faint peppermint odor. Does not 
give Test 702.—Opt. active [+].—P,O, gives a terpene, 
b. p. 170°-3° and a diterpene b. p. 320°-5°, 

Propyl Hexyl Ketone, Pr.CO.C,H,,—M. p. —9°.—Gives no 
NaHSO, comp. 

[+]}Menthone, C,,H,,0.—Similar to [—}menthone. — Oxime 
syrupy. 

+{—]}Menthone, C,,H,,O.— Odor peppermint-like.— D. s. aq.; 
misc. alc. or eth.—Oxime by Test VII-1, m. p. 118°-19°. 

Acetylpropyl Alc., Me.CO.(CH,),.CH,OH.—Slow dist. gives 
unstable anhydride, b. p. 72°-5°.—Misc. aq.; e. s. alc. 
or eth.—NaHSO, comp. e. s. aq. or alc.—May be oxid. 
by CrO, mixture to levulinic ac. 

Methyl Octyl Ketone, Me.CO.C,H,,—M. p. +3-5°.—Odor 
orange-like.—Gives a NaHSO, comp. 

Eucarvol, C,,H,,0.—Boiled w. conc. sol. of KOH in CH,OH 
gives unstable blue color. 

Methyl Benzyl Ketone, Ph.CH,.CO.Me.—Cf. Div. A, m. p. 27°. 

Isopropyl Phenyl Ketone, Pr.CO.Ph.—Phenylhydrazone, m. p. 
71°.—Oxime, m. p. 58°. 

Propiophenone, Ph.CO.Et.—M. p. +21°.—Gives no NaHSO, 
comp.—Oxime melts at 52°-53°. 


- Propyl Phenyl Ketone, Pr.CO.Ph—No NaHSO, comp.— 


Test 702 gives benzoic and propionic acids (Tests 312 
ane Ll je 


{ Pulegone, C,,H,,0.—Odor of pennyroyal (Mentha pule- 
gium).—Gives a NaHSO, comp. (forms very slowly); 
i, ale. or eth.—Opt. active [—].—Adds Br,.—Oxime, 
m,.p. 157° silky ndiv dsssaic.! 

Dihydrocarvone, C,,H,,0O.—Opt. active [+ or —].—Gives 
NaHSO, comp. slowly.—Adds Br,.—Oxime, m. p. 87°-9°. 

p-Methyl Tolyl Ketone, Me.CO.C,H,.Me.—Oxid. by KMnO, 
gives terephthalic ac.—Dibrom-derivative, m. p. 100°. 

Methyl Nonyl Ketone, Me.CO.C,H,,.—Chief constituent of oil of 
rue (Ruta graveolens). Freezes at +6°; m. p.+15°.—Test 
702 gives acetic and pelargonic acids. 

Ethyl Benzyl Ketone, Et.CO.C,H,.—Gives no NaHSO, comp.— 
Test 702 gives benzoic and propionic acids (Tests 312 and 
oll). 

t 2-Methyl-1, 4-Xylyl Ketone, Me.CO.C,H;.Me,.—(Sol. in Test 
VII-2, becomes opaque and yellow after heating 1 min.)— 
No NaHSO, comp.—HE. s. alc. or eth.—Oxime, m. p. 58°. 

m-Methyl Tolyl Ketone, Me.C,H,.CO.Me.—Gives isophthalic *° 

_ on oxid. by alkaline KMnQ,. 





a ~ 


144 





Boiling-point Specific 
(O22); Gravity. 


225-6 0-993(17-5) 


226¢ 0-826(20) 


226 
230-2 
232-3 


235 0-989(0) 
235-6 0-989?3/,, 


235-6 
237-8 
237 - 5-8-5 
237-9 


237-40 
238-9c. 
238-9 


239-40 
240 -5-1 


241-5-2-5 
244-5 


245 -5-6- 5c. 
246-7 (th. i.) 1-019(0) 
246-5 
249 
251 
251-2 
253-5 
254c 0-975(15) 
255-8 


256-60 
259 (th. i.) 0-978(15) 


259 0-957(19) 
259 1-052(15) 
259 


GENUS VII, DIV. B. 


(ORDER I, SUBORDER I.) 





KETONES.—Colorless and Liquid. 


Isobutyl Phenyl Ketone, Bu.CO.Ph.—Test 702 gives benzoic and 


isobutyric acids —Gives no NaHSO, comp.—Oxime, m. p. 
74°, 

{ Caprone, (C,H,,),.CO.—M. p. 14-6°.—Gives no NaHSO, comp. 
—Sol becomes opaque and the undissolved drop deep yel- 
low in Test VII-2 (This is the highest symmet. fatty 
ketone in its series known to give Test VII-2.) 

Diisoamyl Ketone, (C,H,,),..CO.—Yellow oil. 

Diethylacetophenone, Ph.CO.CHEt,. 

p-Tolylacetone, Me.C,H,.CH,.CO.Me.—Gives no NaHSO, comp. 
—Oxime, m. p. 90°-1°. 

Acetylmesitylene, Me.CO.C,H,.Me,. 

Benzylacetone, Ph.CH,.CH,.CO.Me.—Test 702 oxid. to benzoic 
and acetic acids.—Gives NaHSO, comp., rather d. s. aq. 

Isopropyl Tolyl Ketone, C,H,.CO.C,;H,,—Oxime, m. p. 92°. 

Ethyl p-Xylyl Ketone, Et.CO.C,H;.Me,. 

Butyl Phenyl Ketone, Bu.CO.Ph. 

Ethyl p-Tolyl Ketone, Et.CO.C,H,.Me.—Nitration w. fuming 
HNO, gives comp. having m. p. 50°-1°.—Oxime, m. p. 86-7°. 

Allylacetophenone, Ph.CO.CH,.C,H,.—Adds Br, easily. 

a-Methylbenzylacetone, Me.CO.CH(Me)(C,H,). 

Ethyl m-Xylyl Ketone, Et.CO.C,H;.Me,.—Phenylhydrazone, m. 
p 126°.—Oxime, m. p. 72°. 

2-Isopropyl-1, 4-Xylyl Ketone, C,H,.CO.C,H,.Me,.—Odor like 
mushrooms.—Oxime, m. p. 76°. 3 

Benzoyltrimethylene, Ph.CO.C,H;.—Br acts only at high temp. 
—Oxime, lft. fr. lgr., m. p. 90°-2°. 

Isoamyl Phenyl Ketone, C,H,,.CO.Ph. 

4-Isopropyl 1, 3-Xylyl Ketone, C,H;.CO.C,H;.Me,.—Oxime, m. p. 
oT 


{-Methylhydrindone, C, ,H, ,0.—Peppermint odor.—KMnO,oxid. 
to phthalic ac.—Sol. in cone. H,SO, fluoresces blue-violet. 

Methyl o-Xylyl Ketone, Me.CO.C,H;.Me,.—E. s. alc. or eth.— 
KMn0O, oxid. to p-xylic ac.—Oxime, m. p. 85°. 

Methyl Pseudocumyl Ketone, Me.CO.C,H,.Me,.—M. p. 10°.— 
E. s. ale. and eth. 

2-Propyl 1, 4-Xylyl Ketone, Pr.CO.C,H;.Me,.—Aromatic oil.— 
Oxime, m. p. 47°. 

4-Propyl 1,3-Xylyl Ketone, Pr.CO.C,H,;.Me,.—E. s. alc. or 
eth.—Odor turpentine-like. 

Xylitone, C,,H,,O0.—Geranium odor.—I. aq.—Easily oxid.— 
KMn0O, gives CO,, acetic, and a-dimethylsuccinic acids.— 
Resinified by cone. acids. 

Methyl a-Duryl Ketone, Me.CO.C,H.Me,.—E. s. alc. or eth. 

p-Acetylcumene, C;H,.C,H,.CO.Me.—Nitrates to comp. having 
m. p. 49°.—Oxime, m. p. 70°-1°. 

4-Isopropyl 1,2-Xylyl Ketone, Pr.CO.C,H;.Me,. — Turpentine 
odor.—Oxime, m. p. 68° 

Methyl o-Cymyl Ketone, Me.CO.C,,H,;.—Aromatie oil. 

p-Acetylpropylbenzene, Me.CO.C,H,.Pr.—Oxid. by alkaline 
KMn0O, gives terephthalic and benzoic acids. (Tests 318-3 
and 312.) 

2-Isopropyl 1, 4-Isocymyl Ketone, Pr.CO.C, ,H,,.—Oxime is oily. 

Benzoylcyclobutane, C,H,.CO.Ph.—Oxime, d. s. lgr., m. p. 92°. 

Methyl set Ketone, Me.CO.C,H.Me,.—Phenylhydrazone, 
Mepis. 


Boiling-point 
(Gra ye 


260-5c. 
266-9 
270-7 


270-72 
295-6 
300-4 
305-7 

308-10 


a. 300 
312-14 


314-16 


315-16 
322 (th. i.) 


325-30 


Specific 
Gravity. 


0-944(19) 
1-134(0) 


0-826(17) 
1-108(0) 


1-076(0) 


1-062(0) 


1-088(17-5) 


GENUS VII, DIV. B. 145 


(ORDER I, SUBORDER I.) 


KETONES.—Colorless and Liquid. 


Cumylacetone, Pr.C,H,.CH,.CH,.CO.Me.—Oxime, m. p. 56°. 


Ethyl o-Cymyl Ketone, Et.CO.C, ,H,;. 
Phenyl Hexyl Ketone, Ph.CO.C,H.,,. 
oxime, m. p. 55°. 
2-Isobutyl 1, 4-Isocymyl Ketone, Bu.CO.C, ,H,,.—Oxime is oily. 
a-Methyl Naphthyl Ketone, Me.CO.C,,H;.—V. s. alc. or eth_— 
Oxime, m. 145° _—Picrate, iv ale- sol), m.p. 116° -—Br 
substitutes readily. 
Diheptylacetone, Me.CO.CH.(C,H, ;)..—Gives a NaHSO, comp. 
a-Propanoylnaphthene, Et.CO.C,,H;,—V. s. alc. or eth— 
Oxime, m. p. 57°-8° —Picrate, yellow ndl., m. p. 77°-8°. 
a-Isopropyl Naphthyl Ketone, Pr.CO.C,,H;. Ossi i palaos, 
—Picrate, m. p. 66-7°. 
p-Ethylbenzophenone, Ph.CO.C,H,.Et.—Gives isomeric oximes. 
iteopropyl SEDO Ketone, Pr.CO.C,,H;.—V. s. alc.—Oxime, 
maple 2. 
m-Phenyl Tolyl Ketone, Ph.CO.C,H,.Me.—V. s. alc. or eth.— 
Oxime, m. p. 100°-1°. 
o-Pheny] Tolyl Ketone, Ph.CO.C,H,.Me.—Gives isomeric oximes. 
a-Phenyl-m-Xylyl Ketone, Ph.CO.C,H,.Me,—Gives isomeric 
oximes. 
Dioctylacetone, Me.CO.CH.(C,H,,).. 


—Aromatic oil. 
—Lft. m. p. 17°.—Gives an 





NUMBERED SPECIFIC AND SEMI-SPECIFIC TESTS FOR 
THE KETONES. 


[TESTS 701-800.] 


7o1. Colorations with Sodium Nitroprusside. 


Shake five drops of the ketone with 2 cc. of cold water. If the substance does not 
dissolve completely, filter through a wet filter. Add to the clear solution two drops of a 
1% aqueous solution of sodium nitroprusside, and then two drops of sodium-hydroxide 
solution (1:10). Without any unnecessary delay, carefully note the color, and then 
quickly divide the solution into two equal portions, a and b, in small glass “ weighing-tubes.”’ 
To portion 6 add three drops of glacial acetic acid, and immediately note the color. Allow 
both solutions to stand for twenty minutes, and again carefully compare the color of each 
with the color standard. 

Many of the aldehydes as well as ketones of Order I give colorations in this test; 
but its most important practical application is its use as a convenient specific reaction 
for acetone and acetophenone. It distinguishes these ketones readily from all related ketone 
species with which either is likely to be confused. 

In the case of acetone, portion a at first is orange (O), but changes to a clear yellow 
(Y-YT1) within twenty minutes. Portion 6 after the acidification with acetic acid is a red 
(R-RT1) when viewed against .a white background, with a very slight tendency to purple, 
that is most noticeable when the solution is viewed by a strong transmitted light. This 
hue will be found unchanged at the end of twenty minutes, though its intensity will have 
fallen about one tint, i.e. to (RTI-RT2). The persistency of this hue in acetic-acid 
solution is the most characteristic part of the test when used to distinguish acetone from 
its homologues. 

in the case of acetophenone, the color of portion a is at first red with a very slight 
tendency to violet-red, just as in part b of the acetone test after acidification. This changes 
to yellow before the end of twenty minutes. Portion b upon acidification with acetic 
acid changes at once to a strong blue (B-VB), whose hue is not materially changed at the 
end of twenty minutes, although it will have faded nearly one tint to about (BTI-VBT1). 

The most characteristic part of the acetophenone test is the strong blue coloration of 
portion b. Homologues of acetophenone, CH,.CO.R, like methyltolyl- and methylxylyl 
ketone, do indeed give pale violet or bluish colorations, but they are much fainter than 
T3 of the color standard. Fatty-aromatic ketones, like ethyl-phenyl ketone, which contain 
no methyl radical in combination with —CO.R, appear not to give any blue coloration at all. 

[Sodium-nitroprusside solution does not keep well, and should not be more than a 


few days old when used.] 
146 


SEMI-SPECIFIC TESTS FOR THE KETONES. 147 


702. Oxidations with Chromic Acid. 

The aliphatic ketones and alcohols may all be easily oxidized by chromic acid to 
mixtures of fatty acids. These mixtures may then often be resolved into their constituents, 
and the latter identified by forming their silver salts. The method is not especially difficult 
if the acids are not too near one another in the homologous series. 

The oxidation of an unsymmetrical ketone or secondary aleohol may occur in two 
ways; i.e. the splitting of the molecule may take place on either side of the carbonyl or 
hydroxyl group, as illustrated in the following reactions for the oxidation of ethyl-propyl 
ketone: 


CH,.CH,.CO.CH,.CH,.CH, +30 =2CH,.CH,.CO,H, 
or CH,.CH,.CO.CH,.CH,.CH, +30 =CH,.CO,H +CH,.(CH,),.CO,H. 





Frequently, however, the tendency for one of the reactions to take place is so much greater 
than for the other, that only one acid will actually be formed in quantity large enough 
for isolation. 

The chromic acid mixture for these oxidations is prepared by dissolving 10 grms. 
(2 molecules) of crystallized commercial chromic anhydride in a mixture of 60 cc. of water 
and 8 cc. (3 molecules) of concentrated sulphuric acid. Calculate how much of the mix- 
ture will be needed for any oxidation, by assuming that each cubic centimeter contains 
0.05 grm. of “available oxygen,” and that the reaction will take place according to the 
theoretical equation without secondary oxidations—which is not strictly true, since some 
ot the substance will always remain unattacked. Perform the oxidation in a round-bot- 
tomed flask having a capacity of at least five times the volume of the solution. The flask 
should be fitted with a return-flow condenser. It is best to use as much as one or two grams 
of substance for each experiment. Support the flask on a piece of wire gauze, and boil 
briskly until the reduction of the chromic acid is complete. This will not require more than 
an hour if the substance is at all soluble in the mixture. Bumping may be prevented 
by dropping an ebullator tube (cf. p. 223) into the flask before bringing to a boil. The 
oxidation being ended, connect the flask with an inclined condenser; add a fresh ebullator 
tube, and distil rapidly until only a few cubic centimeters of liquid remain in the flask. 
Add 25 cc. more water, and distil again. . 

If only volatile fatty acids are to be sought, place the combined distillates in a flask. 
heat nearly to boiling, without attempting to remove any oily or solid matter that 
may be held in suspension; add an excess of moist silver oxide; and shake persistently to 
hasten the neutralization of the organic acids. Then dilute with hot water,—from 100 to 
1000 cc., according to the solubility of the silver salts that it is expected will be formed,— 
bring to a boil, and filter hot. Repeat the extraction of the residue on the filter with a 
second but smaller quantity of boiling water. Filter. Unite this filtrate with the first, 
and separate the mixed silver salts by fractional crystallization. Since the solubility of 
the salts diminishes as their molecular weight increases, those of higher molecular weight 
will separate first, when a saturated solution is cooled or evaporated.* 

The determination of silver in the salts is made by drying to constant weight at 100° 
in a porcelain crucible, igniting to destroy organic matter, and then weighing the residue of 





* In the case of the mixture of silver caproate and acetate, that is formed when 1 grm. of 
secondary octyl alcohol or methylhexyl ketone is oxidized, a single recrystallization from 
boiling water of the salt that separates from the original hot saturated solution on cooling, gives 
a silver caproate that contains the theoretical percentage of silver. The purification of the 
more soluble silver acetate in the mother liquors requires two or three additional crystalliza- 
tions, in which the first crystals that separate are each time rejected. The separation of two 
salts whose acids lie nearer to each other in the homologous series is more difficult. 


148 SPECIFIC AND SEMI-SPECIFIC TESTS FOR THE KETONES. 


metallic silver. The following table gives the percentage of silver, and the approximate 
solubility of a few of the silver salts of the more important of the fatty volatile acids: 


Per Cent, Ag. 100 Parts of Water Dissolve 
Silver Acetate, Ag COH.Oj 0 64.67 at 20°1.04 pts. | at 80°2.52 pts. 
‘< ~ Propionate, Ag Oe), cae 59.67 ‘Sa 84.68 ve 2.08 %2 
‘*  Butyrate, FW ACA URS). 55.38 EO; 46 cre se bla 
‘«  Isobutyrate, RE a Bae ae he fou, #40) 0675-5 1500 tas 
‘* Valerianate, Agr UC H.O;ees 51.67 eo S0! te ‘70° 0. 64ae 
‘¢ ~~ Methy] ethylacetate, pe ame Mock Ay Ls Liss ** 80° 2 eens 
‘* ~ Tsovalerianate, le gS ae S s 0:25 ts (tO. 3Gee5 
‘*  Caproate, Apc. Ose 48.43 pee si toy ee ‘t. 05345 5 





703. Pyrrol-red Reaction for 7-Diketones. 


Plaee one drop of the ketone if a liquid, or about 0.01 grm. if a solid, in a small test- 
tube, add 1 cc. of glacial acetic acid, three drops of concentrated ammonia, and a freshly 
cut splinter of soft pine wood, and boil gently for half a minute. Remove the splinter from 
the tube and moisten it at once with a drop of concentrated hydrochloric acid. If no pro- 
nounced color is produced in this way, return the splinter to the test-tube, add five drops 
of concentrated hydrochloric acid, and boil again for about one minute. 

y-Diketones of Genus VII, as well as certain species like diethyl diacetylsuccinate 
in other genera whose symbols contain the group —CO.CH,.CH,.CO— undergo condensation 
with ammonia in this test to pyrrol derivatives, which, in the presence of the mineral acid, 
produce an intense red stain upon the wood. With the simple y-diketones like acetonyl- 
acetone the stain appears instantly and with the greatest brilliancy when the wood is 
moistened with hydrochloric acid in the first part of the test. The subsequent boiling with 
hydrochloric acid is, however, necessary to develop the color in the case of bodies like diethyl 
diacetylsuccinate. 


711. Acetone. (Properties tabulated on p. 141.) 


1. Apply the color reactions with sodium nitroprusside described in Test 701, bear- 
ing in mind that since nearly all soluble ketones and aldehydes give colorations of some 
kind when thus treated, the result will be significant only when the colors obtained corre- 
spond closely to the specified hues of the color standard. 

This procedure is to be especially recommended for the preliminary examination 
of aqueous solutions and distillates supposed to contain at least several per cent of acetone. 
In examining such a solution, simply substitute 2 cc. of it for the same volume of the solu- 
tion of definite concentration prescribed in the general directions. Very dilute solutions 
should first be somewhat concentrated by a rectification with the assistance of a small 
distilling-tower. If a solution contains only 1% of acetone, the color of “portion 
a” will at first be yellow-orange (YO), instead of orange; while “portion b,” with acetic 
acid, will give a very pale tint of red, R%'S, instead of R-RT1, which, after standing for 
twenty minutes, will fade to a tone of the same hue, but so pale as to be barely distinguish- 
able. 

2. Place in a dry six-inch test-tube two drops of the ketone and 0.4 cc. of cold water. 
Add 0.4 cc. of benzaldehyde, 2.0 cc. of strong alcohol, and 0.5 cc. of a ten per cent aqueous 
sodium-hydroxide solution. Mix by shaking. Boil very gently over a small flame for 
one minute, counting the time from the moment when the mixture first actually boils. 
Tf no precipitate appears, cool and shake vigorously. Filter off the crystals,* and wash 
~ ¥ If the precipitate, instead of consisting of crystals, is an oil or pasty mass, the procedure 


given requires no modification. Such products usually become crystalline, either during the 
washing with alcohol, or upon the cooling of the solution prepared from the washed oil. 


SPECIFIC TESTS FOR THE KETONES. 149 


with 2 ce. of cold strong alcohol. Recrystallize from 2 cc. of boiling alcohol. Cool, and, 
if necessary, shake persistently until crystals appear. Filter. Wash with 1 ce. of cold 
alcohol. Press on filter-paper or porous tile. Then transfer to a watch-glass and dry 
half an hour or longer at 100°. In taking the melting-point raise the temperature at the 
rate of about one degree in twenty seconds. 

The product formed in this test is dibenzylideneacetone (C,H;.CH:CH),.CO. It 
crystallizes in pale yellow lustrous plates which melt at 111.0°-112° (uncor.). 

Observations on the application of Procedure 2 to aqueous solutions of acetone.—lIf 
a solution contains less than 75% of acetone, take 1 cc. instead of two drops as above directed, 
and add no water. The quantities of the other reagents and the method of procedure 
may be allowed to remain unchanged. The test has been used for solutions containing 
as little as 2% of acetone. But with solutions between 5% and 2%, cooling and shaking 
after heating frequently gives only an emulsion. The addition of 1 cc. of strong cold alcohol 
and shaking will, in such cases, produce a crystalline precipitate, which can then be treated 
in the usual manner. 

If the quantity of crystals obtained from an acetone solution after the first filtration 
is small, wash with 1 cc. of alcohol (instead of 2.0 cc.), and recrystallize from 1 cc. of boil- 
ing alcohol (instead of 2 cc.). If no crystals then appear on cooling and shaking, add 
cold water (0.5 cc.-1.0 cc. is usually enough) until the solution becomes turbid. Shaking 
will then produce crystals. Wash these with 0.5 cc. of cold alcohol (instead of 1 cc.). 
Crystals thus obtained from dilute alcohol will be found to melt at 0.5°-1.5° lower than 
those from strongalcohol. It is, on the whole, advisable to concentrate very dilute acetone 
solutions by distillation rather than to test them by this method at very low concentrations. 

For the detection of traces of acetone by this method, see Vorlander, Hobohm B. 
29, 1840. 


712. Acetophenone. (Properties tabulated on p. 136.) 


1. Apply color reaction 701 with sodium nitroprusside. This is a very satisfactory 
and simple preliminary test. A single drop of the ketone will be enough for the prepara- 
tion of the saturated aqueous solution required. If a negative result is not obtained in 
the experiment, proceed to part (2) of the test, which follows. 

2. Place two drops of the ketone and four of phenylhydrazine in a dry test-tube. Heat 
until the mixture begins to boil. Cool. Add ten drops of glacial acetic acid, then 10 ce. 
of water, and shake. Collect on a filter and wash thoroughly with water. Dissolve in 12 ce. 
of boiling 50 per cent alcohol. Allow to cool. Filter off the abundant precipitate of 
thin flat ervstals, and wash with 2 cc. of cold 50 per cent alcohol. Remove the mother- 
liquor by pressing on a porous tile, and recrystallize from 12 cc. of boiling 50 per cent alcohol. 
Allow to cool slowly. Filter. Wash with 3 cc. of 50 per cent alcohol. Remove the 
mother-liquor on a porous tile, and then dry ten to fifteen minutes at 50°-60° in the dark. 
Determine the melting-point at once. 

Acetophenonephenylhydrazone is a rather unstable body, and is liable to undergo 
slight decomposition in drying. According to Reisenegger and Just, the pure compound 
melts at 105°. As obtained in this test it is perhaps not perfectly pure, as it shows signs 
of softening at 100°, and is completely melted at 103°. 


713. Benzoin. (Properties tabulated on p. 139.) 


Place in a dry test-tube 0.05 grm. of the compound and 0.4 ce. of acetyl chloride. 
Add one drop of concentrated hydrochloric acid. Allow to stand two or three minutes, 
until the vigorous action that will occur ceases. Then heat very gently over a small flame 
until everything is dissolved, removing the tube from time to time to prevent overheating. 
Cool with running water for 5-10 seconds. Add 2.5 cc. of strong alcohol, and then 5 cc. 


150 SPECIFIC TESTS FOR THE KETONES. 


of cold water. Cool well, and shake until the precipitate has separated sufficiently to 
leave the mother-liquor nearly clear. Filter. Wash with 2 cc. of cold dilute alcohol 
(1:2). Heat te boiling with 9 cc. of dilute alcohol (1 : 2). Boil briskly for 10-15 seconds, 
and filter hot from any undissolved residue. Cool and shake as before. Filter. Wash 
with 2 cc. of cold dilute alcohol (1 : 2). Remove mother-liquor by pressing on a piece 
of porous tile. Dry in the air on a fresh piece of porous tile for 20-30 minutes. 

The product in this test is acetylbenzoin, crystallizing in small white needles and 
melting at 79.5-80.5 (uncor.). 


714. Benzophenone. (Properties tabulated on p. 137.) 


Convert 0.05 grm. into benzophenoneoxime, following the regular procedure of Generic 
Test VII-1, except that the period of heating should be extended to ten minutes. After 
the precipitation of the oxime with acid, collect in the point of a small filter, and wash 
thoroughly with 10-15 ec. of cold water applied in small successive portions. Dry for 
half an hour at 100° on a piece of porous tile, and determine the melting-point. 

Benzophenoneoxime is obtained in this test as a flocculent white precipitate soluble 
in acids or caustic alkalies, and melting at 141°-142° (uncor.). 


715. Camphor. (Properties tabulated on p. 139.) 


Convert into camphor oxime by the method of Generic Test VII-1, using twice the 
specified quantities of substance, hydroxylamine-hydrochloride solution, and caustic-soda 
solution, and boiling for one hour instead of for five minutes. In all other details follow the 
general directions literally. After the precipitation of the oxime following the neutralization 
with acid, collect on a very small filter, and wash with at least 10 cc. of cold water applied 
in small portions, the filter being allowed to drain after each addition. Transfer the washed 
precipitate from the point of the filter to a piece of porous tile. Dry at about 50°, and 
determine the melting-point. 

Camphor oxime as obtained by the foregoing method is a white, indistinctly crystal- 
line powder melting at 118°-119° (uncor.). 


CHAPTER X. 
GENUSSY Lipa LGOn@is 


OF 
SUBORDER I, ORDER I. 


(Colorless Compounds of Carbon, Hydrogen, and Oxygen.) 


Genus VIII embraces all species of the suborder that contain the hydroxyl radical 
and have not been described in the foregoing genera. The few ketones that do not react 
readily with hydroxylamine or phenylhydrazine, but meet the requirements of Test VIII 
for alcohols, also receive mention in this section of the tables. 


GENERIC TEST VIII. 


IF THE COMPOUND UNDER EXAMINATION IS SOLUBLE IN LESS THAN FIFTY PARTS 
OF COLD WATER, SEE PROCEDURE 1 BELOW, THE APPLICATION OF PRO- 
CEDURES 2 AND 38 BEING UNNECESSARY. IF IT DOES NOT DISSOLVE IN 
FIFTY PARTS OF COLD WATER AND IS A LIQUID AT THE TEMPERATURE OF 
75°, APPLY PROCEDURE 2 ONLY. IF IT IS NOT SOLUBLE IN FIFTY PARTS OF 
COLD WATER AND IS SOLID AT OR BELOW ‘75°, SEE PROCEDURE 38. 


PROCEDURE 1. 
(The Test by Solubility.) 
If the solubility of the compound in cold water is not already known, deter- 
mine it approximately by the method given on p. 38. 
Any compound, either solid or liquid, that has failed to give the earlier generic 
tests, and which is completely dissolved by fifty parts of water at 20°, can not be a 
hydrocarbon, and should be looked for among the species of Genus VIII. 


PROCEDURE 2. 
(The Test with Sodium.) 

If the compound is not soluble in fifty parts of cold water and is a liquid at 
temperatures below 75°, place about five drops in a narrow glass “ weighing-tube ”’ 
(internal diameter 5-6 mm., length 75 mm.) that has been carefully dried out 
just before use. Support the tube in a vertical position by thrusting it through 
a perforated cork held in a clamp. Place a piece of clean sodium, from which the 
crust has been removed, in a small porcelain dish containing a clear dry hydrocarbon 
oil. Grasping the sodium under the oil with crucible tongs or forceps, cut out a 
bright bit of the metal, about half as large as a grain of wheat (.01—.02 grm.), by 
the aid of a penknife. Seize the fragment with the forceps. Touch it quickly 
to a piece of dry filter-paper to remove most of the adhering oil; and then, without 
delay, drop it into the liquid in the weighing-tube. Allow to stand at the tempera- 
ture of the laboratory for two minutes, and observe any disengagement of gas, or 


change in appearance of the metal. 
151 


152 ALCOHOLS. 


At the end of this time, if the sodium has not disappeared, lower the clamp 
holding the tube so as to immerse the end of the latter in clear paraffin oil, the 
sulphuric acid mixture described on page 218, or any other anhydrous non-volatile 
liquid, previously heated to 75°, and contained in a beaker supported on a lamp- 
stand.* Continue the heating with the bath at 75° for about five minutes, carefully 
watching for the disengagement of gas, and for the disappearance of the sodium, or 
the formation of any incrustation or coloration on its surface. [The test at 75° will 
be omitted in the case of compounds that boil below this temperature.] 

If a brisk effervescence, which continues well sustained until the sodium is 
either dissolved or the contents of the tube are changed to a thick paste, takes 
place in either part of this test, the compound is an alcohol. If the evolution of 
gas is rather slow, but is nevertheless well sustained after the first minute—espe- 
cially if the bubbles approach the size of a small pin-head, or if the sodium shows 
signs of being more than superficially attacked—the compound is very likely to 
be found described with the alcohols. 

If there is no effervescence, and the sodium remains unattacked during both 
parts of the test, the compound is not an alcohol. The same conclusion is usually to 
be drawn whenever there is a very scanty gas evolution which diminishes percep- 
tibly after a minute or two—especially if the bubbles (which may be quite 
numerous) are nearly all microscopic in size. [For remarks on the interpretation 
of doubtful cases, read the ‘‘ observations” on this test on page 154.] 


PROCEDURE 3. 
(The Test by Acetylation.) 


As the test by acetylation is rather long, and is often not indispensable, it is 
well to precede its application by an examination of the descriptions of species 
having the proper melting-point both in Genus IX, 
Div. A, and in Genus VIII, Div. A, Sec. 3. If this 
does not lead to an identification, the employment 
of the acetylation test which follows will sometimes 
become desirable. 

Weigh out accurately in a dry, thick-walled, six- 
inch test-tube, standing upright in the metal support 
usually furnished with analytical balances for such 
uses, 0.1000 to 0.1100 grm. of the unknown com- 
pound. A soft, sound, tight-fitting cork stopper 





= Peer Ss 


e— y-—) 
w 


























* Vig. 4 represents a convenient form of bath for general 
use in heating small tubes to definite temperatures in Tests 
V—1, VII-1, and some of the numbered specific tests, as 
well as in the present procedure. The beaker has a height 
of 10 cm. and a diameter of 7.5 cm. The cover is best made 
from brass, or may be constructed from tinned iron or wood. 
Its three perforations are fitted with cork stoppers to bear 
the tubes and a thermometer. The diameters of the two 
larger perforations should be 23 to 25 mm. The cover, be- 
sides supporting the tubes, protects their upper portions 
from the radiated heat of the bath—which in some tests is 
a considerable advantage—and excludes dust when the bath 
Fig. 4. is laid aside between experiments. 


ALCOHOLS. 153 


should be provided for the tube, and weighed with it. The substance having 
been weighed, drop in upon it—best from a safety pipette especially reserved for 
the purpose (cf. page 236)—0.40 cc. of good acetic anhydride, taking care not to 
allow the anhydride to wet the upper part of the tube, and ascertain the exact 
weight of the anhydride by weighing again. Next remove the cork, which must be 
inserted during the weighings, and hold the lower part of it, which will come within 
the test-tube, in clean hard paraffin that has been melted and heated to above 
100° in a small porcelain evaporating-dish. The immersion in the hot paraffin 
should be continued for about half a minute, or long enough to bring about the 
expulsion of all the small air-bubbles that are seen to detach themselves from the 
cork as the hot paraffin penetrates and fills the minute cavities in its surface. By 
a quick movement shake off most of the excess of paraffin, and then quickly insert 
the cork in the test-tube; press it firmly into place; and hold it until the wax hardens. 

Next thrust the tube through a circular hole cut by a brass cork-borer in a square 
piece of asbestos-board, and place the latter like a cover on a small beaker, so that 
the lower end of the test-tube shall be 1 cm. below the surface of the hot liquid bath 
within. The beaker is filled to within 2 cc. of its lip with paraffin- or cottonseed-oil, 
glycerine, concentrated sulphuric acid, melted paraffin, or some other stable liquid 
of high boiling-point, which has previously been brought to a nearly constant tem- 
perature of between 95° and 105° by heating with a very small flame. Or, if such 
an apparatus is at hand, heat the tube in the covered bath shown in Fig. 4 on page 
152. Continue the heating at this temperature for fifteen minutes. Then remove the 
tube from the bath; cool; unstopper; and add 10 cc. of normal aqueous sodium- 
hydroxide solution from an accurately calibrated 10-cc. pipette. Reinsert the stopper 
firmly, and shake well, cooling with running water from time to time tf the mixture 
tends to become warm. Again remove the stopper and wash it with distilled water, 
collecting the washings in a 75-cc. beaker. If the undissolved reaction product is 
solid or pasty, it may enclose unneutralized acetic anhydride. Hence the lumps must 
now be well crushed and churned up, while still in contact with an excess of alkali, 
by means of a glass rod with a flattened end. Then, rinse the mixture into the 
beaker containing the washings from the stopper, and titrate the free alkali with 
decinormal hydrochloric or sulphuric acid, using phenolphthalein as the indicator. 

Finally, calculate from the data obtained how many milligrams of the acetic 
anhydride heated with the substance have combined with it to form a neutral acetate. 
If the loss of anhydride due to this cause (“acetylation”) exceeds 6 mgrms. when 
0.1000 to 0.1100 grm. of substance was weighed out for the experiment, the compound 
is probably an alcohol, and should be sought in Genus VIII. If the loss of anhydride 
is less than 6 mgrm., it is probably not an alcohol, but may be a species described 
in Genus IX. The calculation of the weight in milligrams of the anhydride con- 
sumed in acetylation will be facilitated by substituting the proper quantities in the 
following formula: 

Wt. in milligrams of anhydride consumed =a—[51.6(d-e)]. 
In this formula: 

a=merm. pure anhydride* weighed out (i.e. apparent wt. X percentage purity). 


* A 100-cc. bottle of an anhydride whose percentage purity has been determined by careful 
titration should be specially reserved for these tests. The reagent will always contain traces 


154 ALCOHOLS. 


b=the exact normility of the approximately decinormal acid. 


Gem Bet a aay - normal alkali. 
d=cce. of above acid equivalent to 10 cc. of above alkali.* 
reek Ona le “required to neutralize alkali remaining uncombined (from 10 ce. por- 


tion) after shaking with products of acetylation experiment. 


Observations on Generic Test VIII. 

“ The Test by Solubility (1)”’ requires no special comment. 

In “ The Test with Sodium (2)” the correct interpretation of the phenomena 
requires good judgment and some experience on the part of the observer. Very 
few commercial specimens of compounds of Genus IX are so free from traces of 
moisture as to give off no gas at all. The ability to make the right decision is most 
quickly gained by examining the behavior of a few representative compounds. 
Heat is employed in the second part of the test, partly to increase the number of 
species to which it is applicable, and partly to make the result more decisive when 
the alcohol is one that is attacked slowly in the cold. The temperature of 75° is 
one at which it is not known that any species of Genus LX is decomposed by sodium. 
At a much higher temperature, however, sodium attacks some of the hydrocarbons 
(e.g. melted anthracene) with considerable violence. Whenever the sodium test 
proves inconclusive, it may be supplemented by Procedure 3. ! 

“The Test by Acetylation (3),” although requiring careful manipulation, will 
give no trouble if directions are closely followed. But if the cork stopper is not 
protected by paraffin, or if the test-tube is heated on a rapidly boiling water-bath 
so that the paraffin softens, or if a rubber stopper is used, the results will be 
worthless. The average accidental loss of acetic anhydride in a properly conducted 
experiment is a little less than 1 mgrm. Heating with the anhydride at 100° for 
fifteen minutes as recommended in the regular procedure is insufficient to com- 
pletely acetylate many of the solid alcohols; but it appears that most monatomic 
alcohols whose acetates are insoluble in cold water will be found to combine with 
very nearly the theoretical quantity of anhydride if the heating is prolonged to 
thirty minutes. 

Procedure 3 is not yates to soluble polyatomic alcohols of Div. A 
Sec. 1, because they usually give soluble acetates which are rapidly saponified 
upon shaking with cold normal alkali. No more acetic anhydride is found to dis- 
appear in an acetylation experiment with ethylene glycol or erythrite, for instance 
than in a blank test. 


of acetic acid, but it will be allowable, for the present purpose to base the calculation of the per- 
centage purity on the assumption that all alkali consumed in the titration is neutralized by 
anhydride only. On account of its peculiar action on phenolphthalein, in titrating acetic 
anhydride, always dissolve it first in an excess of alkali, and then add the indicator and 
titrate back with acid. 


* d= 10 - Calculations will be simplified by recording the numerical value of d on the 
label of the alkali bottle. 


COLORLESS COMPOUNDS CONTAINING OC, H, AND O [SUBORDER I OF ORDER Th 
GENUS VIII, ALCOHOLS. 


DIVISION A, SECTION 1,—SOLID ALCOHOLS SOLUBLE IN LESS 
THAN 50 PARTS OF COLD WATER. 


[Containing all soluble solid species of the suborder not described in the preceding genera.] 


os ia SOLID ALCOHOLS.—Colorless and soluble in less than 50 parts of cold water. 








35-8 7 Pinacone, Me,.C(OH).C(OH).Me,.—B. p. 172°-3°.—Clear cryst. w. faint pecu- 
liar odor.—S. c. aq.; e. s. h. aq. or c. ale.—Boiled w. dil. H,SO, gives a very 
strong peppermint-like odor of pinacoline !—The hot aq. sol. on cooling de- 
posits a hydrate, m. p. 56°. 


46-7 m-Tolylene Alc., C,H,.(CH,.OH),.—V. s. aq.; s. eth.—Oxidation gives iso- 
phthalic ac. (Tests 905 and 318-2). 
49-5 (a)-Dimethylpinacone, Et.C(OH)(Me).C(OH)(Me).Et.—Fairly s. aq.; e. s. alc. 
or eth. 
51-5 Diisopropyl Glycol, Pr.CH(OH).CH(OH)Pr.—B. p. 222°-3°.—E. s. alc., or eth.— 
Combines w. CaCl,. 
52-3 tert.-Butylcarbinol, Me,.C.CH,.OH.—B. p. 112°-3°!—Odor camphorous.— 
‘‘Somewhat”’ s. aq.—Test 702 gives trimethylacetic ac——Very volatile. 
52-3 Methylphenylethylene Glycol, Me.CH(OH).CH(OH).Ph.—E. s. aq., alc., or eth.— 
Tends to separate oily fr. solutions. 
56 Pinacone Hydrate, C,H,,0,.6H,O.—4-sided tbl—Sbl. at ord. temperature.— 
Loses aq. over H,50O,, or on dist., giving pinacone.—H. s. h. aq. 
64 Phthalic Alc., o-C,H,.(CH,.0H),.—Tbl. fr. eth.—V. s. aq., alc., or eth.—Conc. 
H,SO, resinifies—Test 905 gives phthalic ac. 
67-8 Styrolene Alc., Ph.CH(OH).CH,.OH.—B. p. 273° (th. i.).—V..s. aq., alc., or eth. 


—Oxid. by Test 702 to benzoic ac. (Test 312) —65% H,SO, gives hydro- 
carbon, C,,H,.. 


87 Isomannide, C,H, ,0,.—B. p. 274° d.—Hygroscopic cryst., v. s. aq.; 8. alc.; 1. 
eth.—Warmed w. 2 pt. PCl, gives chloride, m. p. 49°. 
102 {[—]Arabite, C,H,.(OH),.—Warty masses, v. s. aq. or h. 90% alc.—Does not 


reduce Fehling’s sol.—Aq. sol. + borax weakly opt. act. [—]. 
112-13 p-Tolylene Alc., C,H,.(CH,.OH),.—Ndl., v. s. aq., alc., or eth.—Oxid. by Test 702 
gives terephthalic ac. (Test 318-3). 


121 Rhamnite, Me.(CH.OH),.CH,.OH.—Triclinic pr. fr. ale.—Opt. active.—V. s. aq. 
or alc.; alm. 2. eth. 
126 } Erythrite, C,H,.(OH),.—B. p. 330°.—Clear cryst.—Taste sweet.—V. s. aq.; 


d.s. ale.; i. eth.—Does not reduce Fehling’s sol —The aq. sol. dissolves CaO 
in the cold. The sol. coagulates on boiling —Schotten-Baumann reaction 
gives tetrabenzoate, mic. cryst. fr. Ac, m. p. 186-5°-7°. 

150 Pinolhydrate, C,,His0,.—B. p. 270°-1°.—S. in 30 pt. aq. at 15°; e.s. alc. or eth.! 
Br, dropped into cooled 5% CHCl, sol. gives cryst. dibromide, d. s. CHCl, 
m. p. 131°-2°.—Warmed w. dil. H,SO, gives oily pinol, b. p. 183°-4°. 


163-4 [—]Mannite, C,H,.(OH),.—Nadl., v. s. aq.; d.s. absolute alc.—Aq. so]. + borax 
is strongly [—]. 
166 +[+]Mannite, C,H,.(OH),.—Taste sweet.—NdL., s. in 6-4 pt. aq. at 18°; v. d. 


s. abs. alc.; i. eth.—Aq. sol. + borax is strongly [+]; alone is opt. i.—Pre- 
vents ppt. of Fe,O, fr. FeCl, by NaOH.—Oxid. by HNO, (cf. Test 205) gives 
no mucic ac. (dif. fr. dulcite).—Sbl. slowly when kept for some time at tem- 
perature somewhat above m. p.—1.8 pt. mannite dissolved in 3.6 pt. conc’ 
HCland shaken with 3.2 pt. benzaldehyde gives cryst. ppt. of mannitetri- 
benzacetol, m. p. 207°; v. d.s.aq.; s. eth.! 


155 


156 


Melting-point 
(O28): 


168 


173 
184-5 


188c, 


188-5 


203c. 
225c. 


234 or 225 (?) 


253 


GENUS VIII, DIV. A, SECT, 1. 


(ORDER I, SUBORDER I.) 


SOLID ALCOHOLS.—Colorless and soluble in less than 50 parts of cold water. 


i.-Mannite, C,H ,.(O0H),.—Plates v. s. h. aq.; v. d.s. abs. ale.—Aq. sol. + borax 


is optically 1. 

Rhamnohexite, Me.(CH.OH) ,.CH,.OH.—Pr., e. s. aq.; s. h. ale.—Opt. act. [+], 

I, 3,5-Cyclohexantriol (Phloroglucite), C,H,.(OH),.—Cryst. fr. aq. Faint but 
pure sweet taste. (Cryst. w. aq. which is easily expelled at 100°.)—E. s. 
aq. or alc.; 1. eth. 

[+ or —]Perseite, C;H,,O;,—Ndl., s. 18 pt. aq. at 18°; d.s. c. ale.—Aq. sol. 
opt. i—Does not reduce Fehling’s solution. 

Dulcite C,H,.(OH),.—Nearly tasteless.—Cryst. s. in about 25 pt. c. aq.; e.s. h. 
aq.; alm. i. alc. or eth.—Oxid. by HNO, (cf. Test 205) yields some mucic 
ac. !—Opt. i. even after addition of borax to sol.—Reactions similar to those 
of mannite. 

rac.-Perseite, C,H,.(OH),;.—Cf. [+ or —] compound, m. p. 188° ¢. 

Inosite, C,H,.(OH),.—Taste sweet.—Efflorescent cryst. w. 2H,O fr. cold aq.; 
cryst. fr.aq. above 50° anhydrous.—4. in 5-7 pt. aq. at 24°; i. abs, alc. or eth. 
—Opt.i— ‘Abit of inosite evaporated to dryness w. a little dil. HNO, on a 
crucible cover gives a reddish-colored mass when treated w. a little ammonia 
and CaCl, and again evaporated.” 

[+] Quercite, C,H,.(OH),.—Cryst. s. in 8-10 pt. c. aq.; d.s. ale.; i. eth. 
Boiled w. dil. H,SO, and MnO, gives pungent quinone odor.—Oxid. by 
HNO, gives oxalic ac., but no mucic ac. (ef. Test 205). 

Pentaerythrite, C.(CH,.OH),.—Tetragonal cryst. s. 18 pt. aq. at 15°.—Opt. i— 
Oxid. by dil. HNO, to glycollic and oxalic acids. 





SMLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER J]. 
GENUS VII, ALCOHOLS. 


DIVISION A, SECTION 2,—SOLID ALCOHOLS NOT SOLUBLE IN 
00 PARTS OF COLD WATER. 








seb ae vont Bena point SOLID ALCOHOLS.—Not soluble in 50 parts of cold water. 








24 143-5(15 mm.)| Dodecyl Alc., C,,H,,-OH.—Silvery Ift. fr. dil. alc. 
27-8 s-Tetramethylpinacone, Et,.C(OH).C(OH).Et,.— Alm. i. aq.; 
v. s. alc. or eth. 
33 254 } Cinnamyl Alc., Ph.CH:CH.CH,.OH. — Aromatic hyacinth- 


like odor —D. s. aq.; v. s. alec or eth. Dropping Br in 
cold CHCl, solution gives bromide, m. p. 74°; 1. aq.; e. Ss. 


alc. or eth. 
34 223 (th. i.) GN el none Me.C,H,.CH,.OH.—S. 100 pt.c. aq.; e.s. alc. 
or eth. 
35 218 Terpineol, C,,H,;,0H.—Cf. Div. B, 2, b. p. 218°.—Lilac odor! 
38 167(15 mm.) | Tetradecyl Alc., C,,H...OH. 
41-2 Dihexylcarbinol, (C,H,,),.CH.OH.—V. s. CHCl, or bz. 
42 210 +[—]-Menthol, C,,H,,.OH.— Cryst. w. strong peppermint 


odor!—D. s. aq.; e. s. ale, eth., or conc. HCl.—May be 
identified by conversion into its benzoate of m. p. 54-5°. 
(Cf. Beckmann, A, 262, 31.) 


42 dist. Phenylbenzylcarbinol, Ph.CH,.CH(OH).Ph.—Boiling w. 20% 
H,SO, gives stilbene. 

45 258-8 Anisic Alc., p-MeO.C,H,.CH,.OH.—Conc. H,SO, gives a reddish 
resin.—Oxid. by dil. HNO, gives anisic ac. 

50 344 + Cetyl Alc., C,,H,,0.—Cryst. in small lft. fr ale-—(When 
fused gives off H easily in Test VITI-2.) 

51 Piperonyl Alc., CH,O,.C,H,.CH,.OH.—Dec. on dist. w. forma- 


tion of piperonal (heliotrope odor) !—Long cryst. not vol. 
w. st.—D. s. c. aq.; v. 8. alc. or eth. 


52-3 p-Phenyltolylcarbinol, Me.C,H,.CH(OH).Ph.—Silky ndl. 
52-3 tert.- Butylcarbinol.—Cf. Sec. A. (‘‘Somewhat s. aq.’’) 
54-4-5 220d. a-Oxyhydrindene, C,H,.OH.—Naphthalene-like odor. 
59 210-5(15 mm.) | Octadecyl Alc., C,,H;,,.0H.—Silvery lft. fr. alc. 
59 217 sha ieerk ri) Me.C,H,.CH,.OH.—D. s. c. aq.; e. s. ale. or 
eth. 
60 303c. a-Naphthylmethyl Alc., C,,H,.CH,OH.—Ndl., somewhat s. 
. aq.; ¥. 8: ale or. eth, 
67 -5-8 297-8 Benzhydrol, Ph,.CH.OH.—Silky ndl., s. in 2000 pt. c. aq.; 


v. s. alc. or eth.—Kasily oxid. in Test 702, giving ben- 
zophenone (Test 714). 


68-9 Carnaubyl Alc., C,,H,.OH.—CrO, gives carnaubic ac.—Fr. 
dil. alc. cryst. w 73-3% aq. 
69 Ditolylcarbinol, (C;H,),.CH.OH.—I. aq.; v.s. alc. 
75 220(15 mm.) | Cetene Glycol, C,,H;..(0H),.—I aq.—Cryst fr h. alc 
75-6 Dilauryl Alc., (C,,H,,),.CH.OH.—Tbl. fr. eth. 
79 | Ceryl Alc., C,,;H,;.0H.—S. alc—Heated w. soda-lime gives 
cerotic ac. 





157 


158 GENUS VIII, DIV. A, SECT. 2. 


(ORDER I, SUBORDER 1.) 





Melting-point B oiling-point 
(C.°). (Coy; 


SOLID ALCOHOLS.—Not soluble in 50 parts of cold water. 





80-0-5 @-Naphthylmethyl Alc., C,,H,.CH,.OH.—Lft. e. vol. w. st.— 
V. iG. ¢24030e. Seale or-eth: 


82 Cerosine, C,,H,,O.—Lft. i. c. ale.; d.s.h. eth.; alm. i. c. eth. 
84-5 Dipalmitylcarbinol, (C,,H;,),.CH.OH.—Silky cryst. fr. alc. 
85 Myricyi Alc., C;,H,,.0H (fr. carnauba wax).—Small ndl- 
fr. eth.—W. soda-lime at 200° gives melissic ac. 
90 Methyl-p-tolylpinacone, C,,H,,.(OH),.—Sbl.—Hexagonal tbl. fr. 
alc.; 1, aq.,.v. 8. ale. or eth, 
101-4 Coccerylic Alc., C;,H,.0,.—Cryst. powder fr. ale.—Oxid. by 


CrO, in Ac sol, gives pentadecylic ac.—(Fr. cochineal.) 


Isohydrobenzoin, C,,H,,.(OH),.—Cryst. fr. aq.; efflorescent.— 
S. in 526 pt. aq. at 15°, or 820 pt. at 100°; e. s. ale. or 
eth.—Oxid. by Test 702 gives benzoic ac.—Diacetate (fr. 
acetyl chloride), lft. fr. h. ale.; m. p. 117°-18°. 


Acetophenonepinacone, (Ph.C(OH).Me)..—Ndl., i. aq.; e. s. 
alc. or eth.—In tube at 280° gives acetophenone and 
methylphenylcarbinol—Acetic anhyd. gives a _hydro- 
carbon, C,,H,,. 


Quebrachol, C,,H,,.0H. — Lft. fr. ale——Cryst. also w. x H,O 
(easily lost).—I. c. aq: or alkalies; v. s. eth., bz., or ace- 
tone.—A sol. in CHCl, shaken w. equal vol. of H,SO, (sp. gr. 
1-76) becomes purple-red after 5 minutes. 


Phytosterine, C,,H,,.0H. — (In peas, beans, etc.) — From 
CHCl, or eth. in ndl.; cryst. fr. dil. ale. w. 1H,0.—S. in 
6-65 pt. eth. at 20°.—Color reactions w. H,SO, same as 
for cholesterine. (Cf. m. p. 148-5°.)—Acetate, lft. fr. alc., 
m, psi120°. 

Retenefluorene Alc., C,,H,,,OH.—Silky ndl., fr. ale.— Alm. 
i. aq.; e. s. ale.—Oxid. gives retene ketone.—Acetate, 
m. p. 70°-1. 

Paracholesterine, C,,M,,00H.—(In Aethalium  septicum.)— 
Cryst. w. aq. fr. dil. alc.; silky ndl. fr. eth. or CHCl,; i. aq. 
—Gives same color reactions as cholesterine w. H,SO, in 
CHCl, sol. 


Isocholesterine, C,,H,,.0H.—(In suint.)—Gelatinous flocks fr. 
alc., d.s.c. alc.; e. s. h. ale. or eth.—Does not give the 
cholesterine reaction w. H,SO, and CHCl, but gives a 
brown color.—When evaporated w. a few drops of conc. 
HNO, leaves yellow spot which becomes yellow-red w. 
ammonia. 

Hydrobenzoin, Ph.CH(OH).CH(OH)Ph.—B. p. a. 300°.—Ad- 
amantine lft. fr. dil. alc.; s. in 400 pt. c., or 80 pt. h. 
aq.; e. s. h. ale-—Oxid. by CrO; gives benzaldehyde.—E. 
acted upon by PCI, in cold.—Heated w. acetyi chloride or 
anhydride gives diacetate, pr. fr. eth., d. s. c. ale., m. p. 
134°. 

Cholestol, C,,H,,0. — Ndl.— Dist.— With CHCl, or acetic 
anhyd. and H,SO, gives the same colors as cholesterine. 


Cupreol, C,,H,,.0H.—(In cinchona barks.)—Cryst. w. aq. 
which is lost in desiccator.—I. aq.; e. s. eth.—CHCl, sol. 
shaken w. H.SO, (sp. gr. 1-76) gives blood-red color.— 
Opt. active [-— ]. 

{ Cholesterine, C,,H,,.OH.[-+H,0, lost over H,SO,].—Dist. in 
vacuo above 360° —S. in 5 pt. h. ale.; ¢.s. eth. or CS,.— 
Dissolve a few cgrms. in 2 cc. chloroform and shake w. 2 cc. 
H,SO, (sp. gr. 1-76). The CHCl, becomes blood-red, cherry- 
red, and finally a beautiful purple color w. strong green fluo- 
rescence in the acid layer. The CHCl, poured into a dish soon 
changes through blue and green to a dirty yellow!—This 
color reaction is also given by several other alcohols stand- 
ing near cholesterine in this section.—Identify by Test 821 ! 


119-5 


120 


125 


132-3 


133-4 


134-4-5 


137-8 


138 


139 


140 


148-5c. 


A RR I 


GENUS Vill, DIV Ay SHOT. 2, 159 


(ORDER I, SUBORDER I.) 





eas te SY ees uaa SOLID ALCOHOLS.—Not soluble in 50 parts of cold water. 





149-50 Paraphytosterine, C,,H,)..OH.—D. s. c. alc.; e. s. eth. or CHCl. 
150 Diphenyltolylcarbinol, Me.C,H,.C(OH).Ph,.— Hexagonal tbl. fr. 
Igr.—E. s. alc. or eth.; less s. lgr.—Dist. undec. 
153 Fluorene Alc., C,;H,.OH.—S. alc., eth., orbz.—W. conc. H,SO, 
turns blue !—Oxid. by Test 702 gives diphenylene ketone. 
154 Ergosterine, C,,Hj..0H.+H,O (from Ergot).—B. p. 185° (20 


mm.).—Pearly lft. fr. ale.—S. in 500 pt. c. or 32 pt. h. 94% 
alc.; s. h. eth. or c. CHCl,.—Sol. in conc. H,SO, is orange- 
red, becoming red and then violet on addition of aq. The 
orange sol. when shaken w. CHCl, does not color the latter. 
(Dif. fr. cholesterine.) 


162 { Triphenylcarbinol, Ph,.c.OH.—B. p. a. 360° undec.— HE. s. alc., 
eth., or bz.—Stable. 
164-5 Phenyltolylpinacone, C,,.H,,.(O0H),.—E. s. bz.; d.s. ale.; s. eth. 


—H. oxid. by CrO, giving phenyltolyl ketone.—Decomposed 
by heating with acids. 

166-7 Chrysofluorene Alc., C,,H,,.CH.OH.—E. s. alc. or eth.—S. conc, 
H,SO, w. red-violet color.—Alc. sol. on addition of conc. 
H,SO, becomes blue. 


168d. Benzopinacone, Ph,.C(OH).C(OH)Ph,.—S. in 39 pt. h. ale-—In 
melting splits into benzophenone (Test 714) and diphenyl- 
carbinol. 

170 Hydranisoin, C,,H,,0,.(0H),.—V. d. s. c. aq., c. ale., or eth.; 
e.s. h. ale.—Oxid. by CrO, mixture to anisic ald. and anisic ac. 

uy ge Illicyl Alc., C,.H,,OH. (fr. bird lime).—B. p. a. 350°.—I. aq.; 
d.s.c. alc. or eth.—M. p. acetate 204°-6°. 

182d. Anthrapinacone, C,,H,,.(OH),.—Nadl. fr. bz. 

183 Homocholesterine, C,,H,.0. (fr. Dalmatian insect powder).— 
V. s. eth. or CHCl,; d.s. ale-—Gives the cholesterine color 
reactions. 

192 sl. d. Camphene Glycol, C,,H,,.(OH),.—Sbl. above 100°.—D. s. h. aq.; 
V..S; ac, or eth,; d.s. ler: 
203-4 + [+ ]}Borneol ( Borneo Camphor), C,,H,;.0H.—B. p. 211°-12°.— 


Sbl. in lft.—Odor scarcely distinguishable fr. that of com- 
mon camphor !—E. s. lgr.; v. d. s. aq.; e. s. ale. or eth.— 
Does not give an oxime. (Dif. fr. ordinary camphor.) 


208-8 [—]}Borneol, C,,H,;,,0H.—Closely resembles the [+] comp.— 
(Occurs in several natural oils.) 
210-5 i-Borneol, C,,H,;.0H.—Closely resembles the [+] comp. 
216 Isoborneol, C, ,H,;,0H.—Closely resembles the [+ ] comp.—Opt. 
active [+ ]. 
258c. Betulin, C,H,O, (fr. birch bark).—Ndl. fr. ale.—Sbl. w. dec. 


—S. in 148 pt. cold, or 23 pt. h. alc.; s. h.eth.; d.s.c. eth.— 
Heated w. acetic anhyd. gives diacetate, pr. s. eth., m. p. 
217°.—Emits odor like morocco leather when strongly heated. 





COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER 1 OF ORDER I]. 
GENUS VIII, ALCOHOLS. 


DIVISION B, SECTION 1,—LIQUID ALCOHOLS (AND 


SOLUBLE 


ETHERS) WITH SPECIFIC GRAVITY LESS THAN 0-90 AT 20°/4?°. 


Boiling-point 
(C32). 
—24 


+10-8 
14 


35 


35 


35-5 
38-9 
39 


45-5 
46 


50 
51-2 
54 
56-7 
61-2 


62-3 


62-3 
63-6 
66 
66 


69c. 


Specific 
Gravity. 


0-725(0) 
0-897(0) 


0-71915/, 


0-859(0) 


0 . 16350 7h os 


0-747(0) 


0+ 87215/, 
0-77(11) 


0-831(0) 
0-745(0) 
0-834(0) 
0-83(12) 


0-769(20) 


0-755(0) 


0-79815/, . 


0-725(21) 


ALCOHOLS.—Colorless and liquid, with Specific Gravity less 
than 0-90 at 20°/4°. 


Methyl Eth., Me,.0.—Is absorbed in large quantity by c. cone. 


H,SO,; the sol. on dil. w. aq. evolves the gaseous ether un- 
changed. 

Methyl Ethyl Eth., Me.0.Et.—Odor ethereal. 

Ethylene Oxide, C,H,O.—Misc. w. aq.—Aq. sol. reduces Tollen’s 
reagent.—f Gives ppt. of MgO after long standing w. cone. 
MgCl, sol—W. HCl gives chlorhydrine.—W. aq. and Na 
amalgam gives C,H,;.OH. 

{ Ethyl Eth., Et,.0.—Mobile liq. of ethereal odor; s.in 12 pt. 
aq. at 17-5°. 

Propylene Oxide, Me.(CH.CH,).0.—S. in 3 vol. aq.; misc. w. 
alc. or eth.—Heated w. aq. gives propylene glycol_—Heated 
w. conc. MgCl, sol. ppts. MgO.—Reduced by aq. and Na 
amalgam to isopropyl! alc. 

Vinyl Ethyl Eth., C,H,0.Et.—Gives Test 901.—Distil w. dil. 
H,SO,. The distillate gives reactions for acetaldehyde and 
ethyl ale. (Cf. Tests 111 and 814.) 

Methyl Propyl Eth., Me.O.Pr. 

Vinyl Eth., (CH,:CH),.0.—Gives Test 901.—Probably gives 

some acetaldehyde when dist. w. dil. H,SO,. 

1 Methylal, CH,.(OMe),.—Described in Genus I. 

Methyl Allyl Eth., Me.0O.C,H,.—Gives Test 901.—B. p. dibro- 
mide, 185°. 

1, 3-Propylene Oxide, (CH,.CH,.CH,).0.—B. p. a. 320°.—Misc. 
w. aq.—Boiled w. conc. aq. KOH gives polymeric oxides. 
Isobutylene Oxide, Me,.(C.CH,).0.—Combines w. aq. w. evol. of 

heat, giving isobutylene glycol. 

Ethyl Isopropyl Eth., Et.0.C,H,—Dec. by 1% H,SO, at 150° 
into its constituent alcohols. 

s-Dimethylethylene Oxide, (Me.CH.CHMe):0O.—Unites quickly 
w. h. aq. to form corresponding glycol. 

Methyl Propargyl Eth., Me.0.C,H..—Gives lemon-yellow gelati- 
nous ppt. w. ammon. AgNO,! 

Ethyl Isopropenyl Eth., Et.0.CMe:CH,.—Dec. by 1% H,SO, 
quickly and completely in the cold into acetone and ethyl 
ale. (Cf. Test 711-1.) 

Allylene Oxide, Me.(C:CH).O.—S. aq. but separated fr. sol. by 
K,CO,.—Very stable. 

Ethyl Propyl Eth., Et.0.Pr. 

Ethyl Allyl Eth., Et.0.C,H,.—Gives Test 901.—Dec. by heating 
w. 2% H,SO, to ethyl and allyl alcohols (cf. Tests 814 and 
811). 

t+ Methyl Alc., Me.OH.— Misc. w. aq.— Odor alcoholic. — 
Identify by Test 819! 

Isopropyl Eth., (C,H,),0. 





160 





Boiling-point 
(C.°). 


78 


78°4 


80 


81-2 


82-8c. 


82-9c. 


83-4 


90-7 (th. 1.) 


94-3 
96- 6c. 


97-Ac. 


99-8 


101-8 


104-5-6 


106-5 


112-5 


114 
115-16 


116-5 
117 
117c. 


117-6 
118-5 


Specific 
Gravity. 


0-875(0) 


0.794157... 


0-833?9/, 


0-880(0) 


0-789?°/, 


0-78076/, 


0-891(0) 
0-744(21) 


0-805(18) 
0-871(0) 


0-804?°/, 


0-827(0) 


0-814(15) 
0-874(0) 
0-817(0) 
0-833(0) 


0-840?, 
0-8342°/, 
0-832(0) 
0-873(0) 
0-8107°/, 
0-839(0) 


0-824(0) 


GENUS VIII, DIV. B, SECT. 1. 


a 


161 


(ORDER I, SUBORDER I.) 


ALCOHOLS.—Colorless and liquid, with Specific Gravity less 
than 0-90 at 20°/4°. 


I,4-Oxypentane, Me.(CH.(CH,),):0.—S. in 10 pt. c. aq.; 
more s. c. than h.; v. s. alc. or eth_—Not attacked by aq. 
at 200°.—When heated w. a 60% HBr sol. gives C,H, ,Br3. 

t+ Ethyl Alc., Et.OH.—Odor alcoholic.—Misc. w. aq.—Identify 
by Test 814! 

Ethyl Propargyl Eth., Et.0.C,H,—Penetrating odor.—D. s. 
aq.; misc. alec.—Unsat.—Gives yellow ppt. w. ammon. 
CuCl.—Heated w. 1% H,SO, gives propargyl and ethyl 
alcohols. 

Pentamethylene Oxide, (CH,),.0.—Less s. in h. than c. aq.; 
misc. alc. or eth.—Does not unite w. aq. at 200°. 

{Isopropyl Alc., Me.CH(OH).Me.—Misc. w. aq.—Test 819-1 
gives amber ring.—Test 801 applied in the cold to a 1% 
aq. sol. gives an immediate ppt. of 1odoform.—lIdentify 
by Test 818! 

| Trimethylcarbinol, Me,.c.OH.— M. p. 25°.—V. s. aq.— 
Deliq. — Odor mild alcoholic.— The color produced in 
Test 819 resembles that given by methyl alc.!—Does not 
give iodoform in Test 801. 

Glycol Dimethyl Eth., C,H,.(OMe),.—HI gas gives glycol and 
methyl iodide. 

t Propyl Eth., Pr,O.—Gives Test 907. 

Allyl Eth., (C,;H,;),.0.—Gives Test 901. 

} Allyl Alc., CH,:CH.CH,OH.—Odor very penetrating and 
mustard-like !—Misc. aq.—Gives Test 901.—Test 819-1 
gives a brown ring.—Identify by Test 811! 

{ Propyl Alc., Pr.OH.—Odor mild alcoholic.—Misc. aq.—— 
Test 819-1 gives amber-colored ring.—Identify by Test 
820! 

t sec.-Butyl Alc., Me.CH(OH).CH,.Me.—Odor mild alcoholic. 
—E. s. aq.—1% aq. sol. gives some iodoform in the cold 
after a few seconds by Test 801.—Test 819-1 gives a pale 
lemon-yellow ring below a pale rose-red ring. 

{+ Dimethylethylcarbinol, Me,.C(OH).Et.—Odor mild alcoholic. 
—Not v. s. aq.—Color given in Test 819-1 is similar to 
that from methyl alc.—Does not give iodoform in Test 801. 

1,5-Oxyhexane, Me.(CH.(CH,),):0.—Odor ethereal_—Rather 
d. s. aq.—Does not unite w. aq. at 230°.—Combines w. 
HCl to form its chlorhydrine. 

ft Isobutyl Alc., Me,.CH.CH,.OH.—Odor alcoholic.—sS. in 10-5 
pt. aq.—Test 819-1 gives amber-colored ring.—Identify 
by Test 817! 

Methylisopropylcarbinol, Me,.CH.CH.(OH)Me.—Oxid. by Test 
702 w. cold, very dil. CrO, gives acetone, methylisopropyl 
ketone, and acetic acid. 

Vinylethylcarbinol, CH,:CH.CH(OH).Et. — Unsat. 
901.) 

Methylallylcarbinol, CH,:CH.CH,.CH(OH).Me.—S. in 8 pt. aq. 
—Oxid. by KMnO, gives 7-pentenylglycerine. 

Diethylcarbinol, Et,.CH.OH. 

Crotyl Alc., Me.CH:CH.CH,.OH.—See Test 901. 


{ Butyl Alc., C,H,.OH.—Odor alcoholic.—S. in 12 pt. aq.— 
Identify by Test 813! 

Dimethylisopropylcarbinol, 
odor. 

Methylpropylcarbinol, Me.CH(OH).Pr.—S. in 6 vol. aq.—lIs 
said to give iodoform in Test 801. 


(Cf. Test 


Me,.(C;H,)C.0H. — Camphorous 





162 


Boiling-point 
(CoN 


119-5 
120-1 
123¢. 
123 
123-5 
128 
128-7 
130 


130 


130-1 
131 


134 
135c. 
136 


137 


137-8 (th. i.) 


138-9 


140 


140: 3c. 


140-2 


147 


147-8 


148-50 


150 
15lc. 


154 (th. i.) 


154 











Specific 
Gravity. 


0-844(0) 
0-835(0) 


0-824(20) 


0-863(0) 
0-838(0) 
0-833°/, 


0-8102°/, 


0-827(0) 


0-868(18) 
0-834(0) 
0-833(0) 


0+828(0) 

0-34218/,, 
0-829?/, 
0-82329/, 
0-840(20) 


0-838(0) 


0-819(17-5) 


0-876(0) 
0-830(15) 


0-820(20) 


GENUS VIII, DIV. B, SECT. 1. 


(ORDER I, SUBORDER I.) 


ALCOHOLS.—Colorless and liquid, with Specific Gravity less 
than 0-90 at 20°/4°. 


Dimethylallylcarbinol, Me,.C(OH).C,H,.—Oxid. by Test 702 
gives acetone (Test 711), formic ac., etc. 

Pinacoline Alc., Me,.C.CH(OH).Me.—M. p. 4°.—Silky ndl. w. 
camphorous odor. 

Methyldiethylcarbinol, Me.C(OH).Et,.—Test 702 gives acetic 
ac. (Test 311). 

Dimethylpropylcarbinol, Me,.(Pr).C.OH.—Test 702 gives acetic 
and propionic acids. 

Glycol Diethyl Eth., C,H,.(OEt),. 

Ethylisopropylcarbinol, Et.CH(OH).Pr. 

act. Amyl Alc., Me(Et)CH.CH,.OH.—Test 702 gives valerianic 
and acetic acids. 

Dimethylisobutylcarbinol, Me,.C(OH).C,H,. — V. d. s. aq. — 
Test 702 gives acetic and isobutyric acids (Test 311). 

{Isoamyl Alc., Me,.CH.(CH,),.0H.—Odor disagreeable, pro- 
voking coughing.—S. in 30-4 pt. aq. at 22°.—Burns w. 
smoky flame.—A few drops warmed w. x’s of CrO, mix- 
ture gives at first the sweetish and fruity odor of valerianic 
aldehyde, soon followed by the unpleasant odor of iso- 
valerianic ac.!—Warmed w. 14 pt. conc. H,SO, gives a 
red sol. 

Methylisobutylcarbinol, Me.CH(OH). Bu. 

2,3, 3-Trimethylbutanol(2), Me,.C.CMe,.0H.—Odor camphor- 
ous.—M. p. 17°.—Hygroscopic, giving a hydrate, m. p. 
83°. 

a-Ethylallyl Alc., Et.C;H,.OH.—Unsat. (Cf. Test 901.) 

Ethylpropylcarbinol, Et.CH(OH).Pr. 

Methylbutylcarbinol, Me.CH(OH).Bu.—Oxid. by Test 702 
gives acetic and butyric ac. 

Hexenyl Alc., C,H,,0.—Odor pungent and peppermint-like. 
—HE. s. & aq. 

Amyl Alc., C,H,,OH.—I. aq.—Test 702 gives valerianic ac. 
(very unpleasant odor). 

Methylcrotylcarbinol, Me.CH(OH).C,H,—D. s. 
(Cf. Test 901.) 

Diisopropylcarbinol, (C,;H,),.CH.OH.—Oxid. by Test 702 gives 
diisopropylketone, isobutyric ac., and acetone. 

Methylethylpropylcarbinol, (Me)(Et)(Pr).C.OH.—Test 702 gives 
acetic and propionic acids. 

Triethylcarbinol, Et,.C.OH.—Test 702 gives acetic and pro- 
pionic acids and diethyl ketone. 

Methylpropylcarbincarbinol, (Me)(Pr).CH.CH,.OH.—Test 702 
gives methylpropylacetic ac. and methyl propyl ketone. 

Ethylisobutylcarbinol Et (Bu).CH.OH.—Test 702 gives acetic 
and isovalerianic acids, etc. 

Methylisoamylcarbinol, (Me)(C,;H,,).CH.OH.—Odor like fusel 
oil.—Oxid. by Test 702 gives methyl isoamyl ketone, iso- 
valerianic ac., etc. 

Isohexyl Alc., Me,.CH.(CH,),.0H. 

Diallylcarbinol, (C,H,),.CH.OH.—Alm. i. aq.—Test 702 gives 
CO, and some formic ac. 

act. Hexyl Alc., Me.CH(Et),.(CH,),.0H (?).—Test 702 gives act. 
caproic ac. 

Dipropylcarbinol, Pr,.CcH.OH.—Test 702 gives propionic and 
butyric acids. 


aq.—Unsat. 


GENUSSVITE DIV. BOSEOT. ¥. 163 


(ORDER I, SUBORDER I.) 


Oe Te 


Boiling-point 
(C.°). 
157c. 

157 
158 -4c. 
160 
160-5c. 
161-5c. 
164-5 
LBP BS 
175-6 


175-8 (th. i.) 
179 


179-5 
190-5 
195-5 (th. 1.) 
194-8 sl. d. 


210-11 
211c. 
214370 (tn, 1.) 
214 sl. d. 


215 (th. i.) 
229-30 


231c. 


Specific 
Gravity. 


0-833(0) 
0-8712°/, 


0-864(0) 


0-830(20) 


0+838?°/, 


0-825(20) 


0-855(20) 
0-878(0) 


0-834(0) 
0-81929/, 


0-835(20) 
0-870(20) 
0-838(0) 
0-868(20) 
0-839(0) 


0-849(0) 
0-842°/, 


0-880(15) 


0-830(20) 


ALCOHOLS.—Colorless and liquid, with Specific Gravity less 
than 0-90 at 20°/4°. 





Hexyl Alc., C,H,,.0H. 

Diethylallylcarbinol, Et,(C,H,).C.OH.—Odor like camphor.— 
Test 702 gives diethyl ketone, etc. 

Methyldiallylcarbinol, Me(C,H,),.C.OH.—Test 702 gives acetic 
ac. (Test 311) and CO,. 

Diethylisopropylcarbinol, Et,(C,;H,).C.OH. 

Cyclohexanol, (CH,),: CH.OH.—M. p. 16°-17°.—Odor like cap- 
ryl ale.—S. in 28 vol. ag.—HNO, oxid. to adipic ac.—CrO, 
oxid. to cyclohexanone. 

Diethylpropylcarbinol, Et,(Pr).C.OH.—Test 702 gives propionic 
and butyric acids. 

Methyldipropylcarbinol, Me(Pr,).C.OH.—Test 702 gives pro- 
pionic and butyric acids. __ 

Methylamylcarbinol, (Me)(C,H,,).CH.OH.—Test 702 gives acetic 
and valerianic acids. 

2-Methylheptene(2)-0l(6), C,H, .OH.—Adds Br directly.—Heat 
several hours w. dil. H,SO, to form the oxide, b. p. 127°-9°. 

Ethyldiallylcarbinol, (Et)(C;H;),.C.0H.—Oxid. by CrO, gives 
oxalic ac. 

{ Heptyl Alc., C;H,..0H. 

{ Methylhexylcarbinol, (Me)(C,H,,).CH.OH.—Test 702 gives 
acetic and caproic acids. | (Cf. foot-note on p. 147.)! 

Ethyldipropylcarbinol, (Et)(Pr,).C.OH.—Test 702 gives acetic, 
propionic, and butyric acids. 

[—] Linalol, C,,H,,O.—(1n origanum and other essential oils.) — 
Agreeable perfume odor!—Adds Br,—KMn0O, oxid. to 
citral, levulinic ac., and acetone. 

Octyl Alc., C,H,,.OH. 

Coriandrol, C,,H,,,.OH.—Fragrant odor!—Shaking w. 5% H,SO, 
gives terpine hydrate.—E. oxid. by KMnQ,. 

Propylhexylcarbinol, (Pr)(C,H,,).CH.OH. 

Diamyl Alc., C,,H,,.OH.—Odor faint. 

Nonyl Alc., C,H,,.OH. 

Anthemol, C,,H,,0.—(Occurs in Roman camomile oil.)—Thick 
liq. w. camphorous odor,—Oxid. by CrO, gives CO, and aq. ; 
by dil. HNO, p-toluic and terebhthalic acids. (Cf. Tests 
905-3 and 318-8.) 

Methylbenzylcarbinol, (Me)(C,H,).CH.OH. 

Geraniol, Me,.C: CH.(CH,),.C(Me): CH.CH,.OH.—B. p. (15 mm.) 
118-20°; still lig. at —15°.—Odor like the geranium and 
rose.—I. aq.; misc. ale. or eth.—Opt. inactive —Oxid. by 
KMn0O, gives acetone and levulinic ac.; by CrO, mixture, 
citral—For identification as its diphenylurethane, cf. 
Journ. f. prakt. Chem. II, 56, 28. 

Decyl Alc., C,,H,,.0H.—Viscous, highly refractive oil.—M. p. 
ete: 


COLORLESS COMPOUNDS CONTAINING ©, H, AND O [SUBORDER I OF ORDER I] 
GENUS VIII, ALCOHOLS. 


DIVISION B, SECTION 2,—LIQUID ALCOHOLS WITH SPECIFIC 


GRAVITY GREATER THAN 0-90 AT 20°/4°. 





Boiling-point 
(C.2). 


67 
102 
114-5 


135 
138 


160-1 


161-2d. 


168-70 


171-2 


176-8 


183-4 


184—5c. 


187-5. 


188-9 


191 
192 


197-7 -5c. 


202-4 
203-5 


Specific 
Gravity. 


1-048(0) 
0-972797, 


0-926(13) 
1-113(18) 


O °O15* 7. 


1-165(0) 


1-136(20) 


1-145(0) 


1 -003(20) 


0-960(15) 


0. 995(0} 


1-040(19- 4) 


0-920(21) 


1-019(0) 
1-125(0) 


1-013 
1-011 


0-950(15) 








ALCOHOLS.—Colorless and liquid, with Specific Gravity 
greater than 0-90 at 20°/4°. 


Hydrofurane (cf. Genus IX, B, 3). 

Dioxyethylene, C,H.O,.—M. p. +9°. 

Propargyl Alc., CH :C.CH,.OH.—Odor agreeable.—S. aq. —-Un- 
sat. (cf. Test 901), and gives an explosive greenish-yellow 
ppt w. ammon. CuCl in Test 906.—Heated w solid KOH 
gives acetylene, CO,, and H. 

Ethyleneglycol Monoethyl Eth., HO.CH,.CH,.OEt. 

Erythrite Anhyd., C,H,O,.—Misc. w. aq.—Reduces h. emmon. 
AgNO, sol.—Ppt’s MgO fr. MgCl, sol. 

Trimethyleneglycol Ethyl Eth., Et.0.(CH,),.0H.—Odor pleasant. 
—V.s. aq. 

Glycid, C,H,0.CH,.OH.—B. p. (15 mm.) 74°-5°.—Misc. w. aq., 
alc., or eth.—Dist. under ordinary pressure gives acrolein 
(Test 112).—Reduces Tollen’s reagent in the cold (Test 101)! 
—Unites quickly w. aq., forming glycerine (Test 816). 

Furfuralcohol, C,H,O.CH,.OH.—D. s. aq.!; e. s. ale. or eth.— 
Very unstable towards mineral acids; becomes green when 
treated w. conc. HCl!—Heated w. solid KOH gives succinic 
ac. (Test 320), CO,, etc. 

Glycerine Eth., (C;H,)..0;.—Misc. w. aq., alc., or eth. !—At 100° 
unites w. aq. to form glycerine (Test 816)!—After being 
warmed w. dil. HCl gives ‘‘iodoform reaction”’ and reduces 
Fehling’s sol.—Br acts violently, giving dibromhydrine. 

1, 2-Dihydroxy-2-methylpropane, C,H,,0,.—Heated w. aq. at 
180°-200° gives isobutyric ald. 

2, 3-Dihydroxy butane, C,H,.(OH),. 

Suberyl Alc., (CH,),:CH.OH.—Taste, burning, bitter.—PCl, 
gives suberyl chloride. 

2, 3-Dihydroxypentane, C,H,,0,.—Oxid. by Br aq. gives acetyl- 
propionyl. 

Propylene Glycol, MeCH(OH).CH,.OH.— Taste sweetish: — 
Mise. w. aq.; s. in 12-13 pt. eth—Test 702 gives acetic 
ac. only.—Made into a paste w. ZnCl, and ignited as in 
Test 816 for glycerine gives propionic ald. 

s-Diethylglycerine Eth., C,H,,0;. 

1, 2-Dihydroxybutane, C,H,.(OH),.—E. s. aq. 

+ Ethylene Glycol, CH,(OH).CH,(OH).—Somewhat viscous liq. 
—Misc. w. aq.; v. 8s. alc.; d.s. eth.—Solidifies abt. — 20° 
and then melts at —17.4°.—Ignited w. KHSO, as in 
acrolein test for glycerine gives acetaldehyde. (Cf. Tests 
816, 112, and 111.) 

Methylphenylcarbinol, (Me)(Ph).CH.OH. 

Butanediol (1, 4), C,H,.(OH),.—Viscous. 


~ 


164 


Boiling-point 
Ory 


204 


204: 7c. 


206-7 
212 
214 (th: i.) 


217 


218 


221 


220-5 
235 


225-30 
240d. 


246 - 6c. 

247-5 
250 
254 


290 
290c. 


327 


Specific 
Gravity. 


1-126 


1-043?9/, 


1-034(21) 
1-053(18) 


1-036(0) 


0-936(20) 


1-000(0) 


1-008(18) 


1-101(25) 
0-978(15) 
1-120(23) 
1-132(0) 
1-0442°/, 


1-138 
1-2607%/, 


1-062(16-5) 


GENUS VIII, DIV. B, SECT. 2. 165 


(ORDER 1, SUBORDER I.) 





ALCOHOLS.—Colorless and liquid, with Specific Gravity 
greater than 0:90 at 20°/4°. 


Butanediol(1, 3), C,H,.(OH),.—V. s. aq.; i. eth.—Oxid. gives 


oxalic and acetic acids and crotonic ald. 


Tt Benzyl Alc., Ph.CH,.OH.—Odor faintly aromatic.—S. in 
25 pt. aq. at 17°.—Oxid. by Test 702 gives benzoic ac. 
(Test 312).—(Unless freshly prepared is likely to contain 
traces of benzaldehyde.)—Identify by Test 812! 

2, 3-Dihydroxyhexane, C,H,,.(OH),. 

Benzylcarbinol, C;H,.CH,.OH. 

{ Trimethylene Glycol, CH,(OH).CH,.CH,(OH).—Viscous; misc. 
w. aq.—f Distilled w. KHSO, as in acrolein test for glycer- 
ine (Tests 816 and 112) gives no color w. the fuchsine- 
aldehyde reagent. (Dif. fr. glycol and glycerine.) 

m-Tolylcarbinol, Me.C,H,.CH,.OH.—Remains liq. at —20°.— 
S. in 20 pt. c. aq. 

1 Terpineol, C,,H,,O.—Separates fr. eth. sol. in transparent 
cryst. w. m. p. 35°. (The commercial product is always 
liq.)—I. aq.; v.s. alc. or eth.—Adds Br,, giving oily bromide. 
Gives a dihydrochloride, m. p. 50°.—The odor when suffi- 
ciently diluted resembles that of lilac flower! 

1,4-Dihydroxypentane, C;H,,.(OH),.—Viscous.—Misc. w. aq. 
or ale, !; 1. lgr. 

s.-Dimethyl Dipropyl Glycol, [(Me)(Pr)C.OH},. 

Phenylpropyl Alc., Ph.(CH,),.0H.—Viscous, d. s. aq.; misc, 
w. alc. or eth.—May be oxid. by CrO, to hydrocinnamic ac. 

Ethyl Glyceryl Eth., CH,(OH).CH(OH).CH,.0.Et. 

Allyl Glyceryl Eth., C,H;.0;.C;H;—S. in 2 or 3 vol. aq.!— 
Unsat. (Cf. Test 901.) 

p-Cuminic Alc., Me,.CH.C,H,.CH,.OH.—Misc. w. alc. or eth.— 
Oxid. by KMnO, to terephthalic and oxypropylbenzoic 
acids.—Persistent boiling w. Zn dust gives cymene. 

Saligenin Methyl Eth., o-MeO.C,H,.CH,.OH. 

Diethylene Glycol, CH,(OH).CH,.0.CH,.CH,.OH.—S. aq. alc. or 
eth. 

Cinnamyl Alc., Ph.CH:CH.CH,.OH.—Aromatic odor like hy- 
acinths.—D. s. aq.; v.s. alc. or eth.—Gives Test 304 easily. 


Triethylene Glycol, C,H,,0,.—Misc. w. aq.; d.s. eth. 


{ Glycerine, CH,(OH).CH(OH).CH,.OH.—Viscous sweet-tast- 
ing syrup.—Misc. w. aq. or alc.; i. abs. eth—Identify by 
Test 816!—(Commercial glycerine usually contains so 
much water that it may begin to boil 100° lower than 
the b. p. given. The temperature will rise nearly to the 
true b. p., however, if the distillation is continued.)— 
[N.B.—Several of the higher homologues of glycerine have 
been prepared. They are syrups, v. s. in water and almost 
insoluble in ether; but as they possess little interest, and 
can not be distilled without decomposition under the usual 
atmospheric pressure, their description is omitted.] 


Dibenzylcarbinol, (Ph.CH,),.CH.OH.—E. s. alc. or eth. 





NUMBERED SPECIFIC AND SEMI-SPECIFIC TESTS FOR 
THE ALCOHOLS. 


[TESTS 801-900.] 
801. The Iodoform Test. 


The more or less ready formation of iodoform when certain aliphatic compounds 
are treated with iodine in dilute alkaline solution, furnishes a qualitative test that has 
found many applications in organic analysis. When the use of this reaction is directed 
in the tables for the purpose of distinguishing between some of the lower boiling liquid 
alcohols and ketones, proceed as follows: 

Prepare a cold aqueous solution containing one drop of the pure compound in each 
cubic centimeter of water. If the test is to be made with a single centimeter of the solu- 
tion, carry it out in a three-inch test-tube (‘‘weighing-tube”). For each centimeter of 
solution used, add two drops of sodium-hydroxide solution (1 : 10); then, drop by drop, 
from a medicine-dropper, a concentrated iodine solution,* until a barely perceptible tint 
of yellow, that persists after standing for several seconds, remains. If too much iodine 
should be inadvertently used, cautiously add just enough more soda to destroy the excess 
of color. Let the mixture stand at the temperature of the laboratory for two minutes. 
Then shake and notice whether any iodoform has separated. 

If no iodoform separates in the cold, immerse the bulb of a small thermometer in the 
solution; heat to 60°, and maintain this temperature for one minute. If the solution 
becomes entirely colorless during the heating, add just enough more iodine to restore 
the trace of yellow that was previously present. If no precipitate appears at once, set 
the tube aside for two minutes before making the final observation. 

In the first part of the test, 7 the cold, tsopropyl alcohol and acetone give none precipr- 
tates of todoform immediately; secondary butyl alcohol rather slowly. Methyl, ethyl, 
propyl, isobutyl, tertiary butyl, isoamyl, and allyl alcohols give no precipitates under the 
same conditions. 

After heating at 60°, ethyl alcohol gives a good precipitate, and allyl alcohol a very scanty 
one. The other compounds mentioned in the preceding paragraph which do not give 
iodoform in the cold, do not give any at 60° within the specified time limit. 

The interpretation here given to the results of the test will not hold for solutions that 
vary greatly from the prescribed concentration. It is applicable, however, in testing the 
saponification distillates obtained by the procedure of Generic Test V-2, B. Under 
other conditions, which were first carefully studied by Lieben,f the delicacy of the reac- 
tion when used for the detection of smaller quantities of ethyl alcohol, etc., may be 
greatly increased. According to Lieben, most compounds containing the CH,.CO.C and 
CH,.CHOH.C groups may be made to yield iodoform by appropriate treatment with 
iodine and alkali; some, like levulinic acid, giving it very readily in the cold. Hence 


* This iodine solution should be kept in stock, and is prepared by rubbing 1 part iodine in 
a mortar with 5 parts of potassium iodide and 15 parts of cold water. 

+ Cf. Lieben, Liebig’s Annalen, Spl. 7, 221.—The lower alcohols and acetone, if in very weak 
solutions, are easily concentrated by distilling through a tower. The first runnings will contain 
nearly all of the organic compound so that the second half of the distillate may be safely rejected, 
The process of “salting out” with potassium carbonate may be combined with distillation, as is 
illustrated in paragraph (i) of Generic Test V-2, B. 


166 


SPECIFIC TESTS FOR THE ALCOHOLS. 167 


while the test is more used than any other as a preliminary reaction for the detection of 
ethyl alcohol and acetone in aqueous solutions, the result requires confirmation by 
additional evidence. 

Iodoform is ordinarily recognized by its peculiar pervasive odor and pale-yellow color, 
though it is said that neither of these properties are characteristic of the chemically pure 
substance. Indeed, under the conditions of the test, the precipitate is at first often prac- 
tically white, and the odor is not always well developed at the moment of formation. An 
iodoform odor, unaccompanied by a precipitate, should never be accepted as satisfactory 
evidence of the presence of any of the compounds giving the reaction. An iodoform pre- 
cipitate, if washed with cold water, dissolved in a little warm and quite dilute alcohol, and 
then allowed to crystallize out very slowly, separates from the solvent in regular hexagonal 
plates of decidedly characteristic appearance, in which the opposite corners of the hexagon 
are connected by straight lines crossing its geometrical centre; or, sometimes, in regular 
six-rayed stars whose primary rays branch into a system of symmetrical subordinate 
rays after the manner seen in frost crystals. 


811. Allyl Alcohol. (Properties tabulated on p. 161.) 


Support a 25 ce. distilling-flask with a long side-tube in a vertical position by a clamp. 
Cool the bulb by surrounding it with cold water. Introduce two drops of the alcohol, 
and then three drops of a solution made by dissolving 1 grm. of chromic anhydride in 
a mixture of 6 cc. of water and 0.8 cc. of concentrated sulphuric acid. The liquids should 
be dropped from a medicine-dropper in such a manner that they will not come in contact 
with the side walls of the flask in falling. Cork quickly. Loosen the clamp, and incline 
the flask so that the lower end of the side tube shall dip into 2 cc. of water contained in 
a test-tube standing in a beaker partly filled with cold water. Boil the solution in the 
flask over a very small flame until it has evaporated nearly to dryness. Loosen the stopper 
before taking away the lamp. 

Mix the aqueous solution in the test-tube with 5 cc. of the fuchsine-aldehyde reagent 
used in Test 112 (1). Allow to stand overnight and observe the color the next morning. 
Mix 2 cc. of the solution with 2 cc. of hydrochloric acid (sp. gr. 1.20), and again observe 
the color. Finally note the color of this acid mixture after it has been diluted with water 
to 100 cc. 

In this test allyl alcohol is oxidized to acrolein. The violet-red coloration which 
makes its appearance within a few seconds after adding the aldehyde reagent, and which 
within ten minutes renders the solution practically opaque, is not characteristic, very 
similar colors being obtained from many other alcohols when treated in the same manner. 
If, however, the color after standing overnight is a red-violet (RV), of such intensity as 
to appear opaque except in thin layers, and if this color upon addition of the hydrochloric 
acid changes to an impure dark yellow or dark yellow-green (about YS2 to YGS2, when 
viewed in very thin layers against a white background), and this color in turn, upon 
the dilution with water to 100 cc. gives a pure blue (BTI, occasionally approximating 
VBTI, the comparison being made in a six-inch test-tube against a white background), 
the compound, if it has the proper physical properties, must be allyl alcohol. 


812. Benzyl Alcohol. (Properties tabulated on p. 165.) 


Place in a 25-50 ce. distilling-flask two drops of the chromic-acid mixture used in 
Test 811 for allyl alcohol, 10 cc. of water, and four drops of the alcohol. Heat over a 
small flame, while shaking, for two or three minutes, until the solution appears distinctly 
greenish; the temperature meanwhile being kept a little below boiling, so that no vapor 
shall escape through the side tube. Next distil, collecting about 2 cc. of distillate in a 
test-tube containing 1 cc. of cold water. Do not use a condenser, but let the extremity 


168 SPECIFIC TESTS FOR THE ALCOHOLS. 


of the side-tube of the flask almost touch the surface of the water in the test-tube. The 
test-tube should stand in a beaker half filled with cold water. When the distillation is 
finished, wash down the sides of the test-tube with 3 cc. of water and 6 cc. of strong alcohol. 
Add one drop of pure phenylhydrazine and boil for half a minute. ‘From this point on, 
follow literally the directions given in part 1 of Test 113 for benzaldehyde. 

The oxidation with chromic acid gives benzaldehyde; and the treatment with phenylhy- 
drazine gives its phenylhydrazone, melting-point 156°. The hydrazone, being rather 
unstable in the light, will sometimes be found to melt one or two degrees below its true 
melting-point. (Benzyl alcohol oxidizes so readily, that specimens which have been ex- 
posed for some weeks to the air will be found to give aldehyde reactions.) 


813. Butyl Alcohol (Normal).* (Properties tabulated on p. 161. 


Convert six drops of the alcohol into n-butyl 3, 5-dinitrobenzoate by the procedure 
given in the first paragraph of Test 814-1. 

To purify the ester, crush the reaction product when cold with a stirring-rod. Dissolve 
it in 10 ce. of ethyl alcohol (2:1). Filter hot if not clear. Cool well, shake persistently, 
and filter. Wash with 3 cc. of cold ethyl alcohol (2:1). Recrystallize from 8 ce. of the 
same alcohol and wash with 2 ce. Spread on a porous tile and allow to become air dry 
in a warm place. Determine the melting-point. 

The ester obtained in this test is distinctly crystalline, has a pearly lustre, and melts at 
64° (uncor.). 


814. Ethyl Alcohol. (Properties tabulated on p. 161.) 


The ready formation of iodoform at 50°-60°—but not in the cold—in Test 801 is 
the most convenient preliminary test for ethyl alcohol. The following very satisfactory 
confirmatory test is, of course, applicable only to a nearly pure alcohol containing not 
more than about 10 per cent of water. The same general procedure with slight modifica- 
tions may be used in the identification of many of the homologues of ethyl alcohol. 

1. Heat together gently in a three-inch test-tube held over a small flame, 0.15 grm. 
of 3, 5-dinitrobenzoic acid | and 0.20 grm. of phosphorus pentachloride. When signs of 
chemical action are seen, remove the heat for a few seconds. Then heat again, boiling 
the liquefied mixture very gently for one minute. Pour out on a very small watch-glass, 
and allow to solidify. As soon as solidification occurs, remove the liquid phosphorus 
oxychloride with which the crystalline mass is impregnated by rubbing the latter between 
two small pieces of porous tile. Place the powder in a dry five- or six-inch test-tube. Allow 
four drops of the alcohol to fall upon it, and then stopper the tube tightly without delay.— | 
[When employing this procedure for the propyl and butyl alcohols, use six drops of the 
alcohol instead of four; for the alcohol must always be present in moderate excess.|— 
Immerse the lower part of the test-tube in water having a temperature of 75°-85°. Shake 
gently, and continue the heating for 10 minutes. 

To purify the ester produced in the reaction, crush any hard lumps that may form 
when the mixture cools with a stirring-rod, and boil gently with 15 cc. of methyl alcohol 
(2:1) until all is dissolved, or for a minute or two.—_{In testing for other alcohols than 
ethyl, all directions for the use of the solvent in this paragraph must be modified as else- 
where specified. Cf. tests for methyl, propyl, butyl, and isobutyl alcohols.]—Filter boiling 
hot if the solution is not clear. Cool. Shake, and filter. Wash with 3 cc. cold methyl 
alcohol (2:1). Recrystallize from 9 cc. of boiling methyl alcohol (2:1). Wash with 





* A preparation from Kahlbaum of Berlin. 

+ This new reagent is listed by C. A. F. Kahlbaum of Berlin at 8 marks per 100 grams, and 
may be obtained in New York from Eimer & Amend. It may also be readily prepared in the 
laboratory from benzoic acid. 


SPECIFIC TESTS FOR THE ALCOHOLS. 169 


2 cc. of the same solvent. Spread out the product on a piece of tile. Allow to become air 
dry, and determine the melting-point. 

Ethyl 3, 5-Dinitrobenzoate, the product in this test, crystallizes in white needles 
melting at 92°-93° (uncor.). 


815. Ethylene Glycol. (Properties tabulated on p. 164.) 


Shake vigorously in a stoppered six-inch test-tube for five minutes, occasionally 
cooling with water, one drop of the alcohol, 0.4 cc. benzoyl chloride, and 5.0 ce. of a 10 
pen cent aqueous solution of sodium hydroxide. Add 10 ce. of cold water. Shake again 
for a few seconds, and then filter. Wash the precipitate with 20 cc. of cold water. Dis- 
solve in 20 cc. of hot dilute alcohol (1 : 1), filtering hot if the solution is not clear. Cool 
and filter. Wash with 4 cc. of cold alcohol (1:1). Dry on a porous tile at the room 
temperature for an hour. 

The ethylene dibenzoate, as obtained in this test, melts at 70.5°-71° (uncor.). The 
melting-point may be slightly raised by repeated crystallization. 


816. Glycerine. (Properties tabulated on p. 165.) 


Of the three tests for glycerine here described, color reaction 1 with pyrogallol has 
the advantage, as a preliminary test, of being rapid and directly applicable to rather dilute 
aqueous solutions, but results by procedures 2 and 3 are more conclusive. 

In testing for glycerine in the presence of other organic compounds, such for example 
as in the aqueous solution resulting from the saponification of an ester by the method 
of Generic Test V—2, the glycerine should first be isolated in a nearly pure state by evap- 
orating to dryness on a water-bath, and extracting the powdered saline residue with a 
mixture of equal volumes of nearly absolute alcohol and ether. Evaporation of the solvent 
will then give a syrup that will often be pure enough for identification by either one of 
the following methods. In the presence of sugars this purification will prove insufficient 
to permit the use of procedures 1 and 3; but method 2 may be safely used. , 

1. Dissolve one drop of the glycerine in 2 cc. of cold water. Add five drops of a one 
per cent aqueous solution of pyrogallol, and 2 cc. of concentrated sulphuric acid. Shake. 
Heat quickly to boiling and boil for 20-25 seconds. Cool immediately with running water. 
Dilute to 20 cc. with strong alcohol in a six-inch test-tube. Without delay compare the 
coloration produced with the color standard, holding the tube in front of a white back- 
ground. 

Glycerine in this test gives a characteristic purplish-red coloration to the alcohol 
that matches VRT1-T2 of the standard. The color fades away after standing for some 
minutes. 

This procedure is directly applicable to quite dilute aqueous solutions if “2 ce. of the 
solution” is substituted for the “drop of glycerine, and 2 cc. of cold water” called for in 
the directions. The color from a one per cent solution will then be found to be as pure, and 
nearly as intense, as when a drop of pure glycerine is taken. The color given by solutions 
containing 0.1 per cent of glycerine is very pale indeed and fades rapidly, but it is still 
quite noticeable, and of the correct hue. Very weak solutions may require heating for 
thirty seconds or more. The presence of sugars, or of certain other polyatomic alcohols 
like erythrite, may obscure the reaction by giving rise to reddish- or yellowish-brown color- 
ations. 

2. Stir up into a stiff uniform paste on a watch-glass, by means of a thin wire, one drop 
of the syrupy compound and 0.5 grm. of powdered acid potassium sulphate. Drop 
the mass into a dry six-inch test-tube supported by a clamp in a slightly inclined position 
on a lamp-stand. Fit the tube with a clean perforated cork stopper carrying a glass gas- 
delivery tube, 20-25 cm. long, and bent downward so that one end is barely immersed 
beneath the surface of 2 cc. of distilled water contained in a second test-tube that stands 


170 _ SPECIFIC TESTS FOR THE ALCOHOLS. 


in a beaker partly filled with cold water. Ignite the sulphate mixture strongly with a 
gas-flame until frothing ceases and the mass is completely liquefied. Test the aqueous 
solution in the second test-tube for acrolein by observing its odor, and by color reaction 
112-1. 

The vapors of acrolein, the dehydration product of glycerine in this test, are remark- 
able for their painfully irritating action on the mucous membranes of the nose and eyes. 
Their effect must not be confounded with that due to sulphur dioxide, which is usually 
formed during the ignition, even in the absence of glycerine. Little difficulty will be found 
in making the distinction by any one who has ever performed the experiment with pure 
glycerine. The phenomena of the color reaction between acrolein and the fuchsine-aldehyde 
reagent are fully discussed under the specific test for acrolein, and are very characteristic. 

Ethylene glycol gives acetic aldehyde, but like trimethylene glycol, erythrite, or man- 
nite, does not give an acrolein odor or interfering color reaction in the fuchsine test- 
This latter reaction is also not seriously interfered with by the small quantities of grape- 
or cane-sugar that remain with glycerine after the purification of a crude glycerine by the 
ether-alcohol extraction referred to in the introduction to this test. Sugars, if present in 
larger quantity, are likely to give confusing colorations, but never any acrolein odor. 

3. Place in a six-inch test-tube one drop of glycerine, 0.4 cc. benzoyl chloride, and 5.0 ce. 
of a 10 per cent aqueous solution of sodium hydroxide. Stopper, and shake vigorously, occa= 
sionally cooling under cold water, until a solid separates. This requires from five to eight 
minutes. Add 10 cc. of cold water, and shake again for ten to twenty seconds. Filter. 
Wash with 20 cc. cold water; then with 10 ce. of a cold mixture of 2 ce. glacial acetic acid 
and 8 cc. water. Crystallize from 15 ce. of boiling dilute alcohol (2 vols. alcohol: 1 volume 
aq.). Filter hot if all does not dissolve on boiling. Cool and shake till a precipitate gathers. 
Filter. Wash with 3 cc. of dilute alcohol (2:1). Dry on a porous tile in the air. 

The product in this test is a white crystalline substance melting at 71°-72° (uncor.). 
It is presumably glycerine tribenzoate, for which several melting-points with the extreme 
values of 70° and 76° are to be found in the literature. 

This procedure is applicable with only slight modification, to not too dilute solutions 
of glycerinein water. Thus, a fair yield of benzoate is obtained when one drop of glycerine 
dissolved in 1 cc. of water is substituted for one drop of pure glycerine as prescribed in the 
directions. It is of course inapplicable in the presence of polyatomic alcohols or other 
substances giving.the Schotten-Baumann reaction. 


817. Isobutyl Alcohol. (Properties tabulated on p. 161.) 


Convert six drops of the alcohol into <sobutyl 3, 5-dinitrobenzoate by the procedure 
given in Test 819-2 for preparing the methyl ester of the same acid. 
The isobutyl ester is obtained in this test in white flocks melting at 83°-83.5° (uncor.). 


818. Isopropyl Alcohol. (Properties tabulated on p. 161.) 


Oxidize four drops of the alcohol with six drops of the chromic-acid mixture used in 
Test 811 for allyl alcohol. The procedure for the oxidation is identical with that given 
for allyl alcohol, except that the vapors are to be conducted into a six-inch test-tube con- 
taining 0.4 cc. of cold water, 0.4 cc. of benzaldehyde, and 2 ce. of strong alcohol. Shake 
and add 0.5 ce. of a ten per cent caustic-soda solution, and boil very gently over a small 
flame for one minute, counting from the time when actual boiling begins. Cool and shake. 
Filter off the crystalline precipitate and wash with 1 cc. of strong alcohol. Boil up with 
1 «c. of strongalcohol. Cool, and shake vigorously, adding from one to four drops of water, 
if necessary, to start the separation of crystals. Filter, and wash with 0.5 ce. of cold ‘alcohol. 
Press on a porous tile, and then dry fifteen minutes at a temperature not above 100°. 

Isopropyl alcohol is oxidized in this test to acetone, which is then condensed with 


See 


SPECIFIC TESTS FOR THE ALCOHOLS. 171 


the benzaldehyde to dibenzylidene-acetone (cf. Test 711-2), crystallizing in pale-yellow 
lustrous plates that melt at 111°-112° (uncor.). 


819. Methyl Alcohol. (Properties tabulated on p. 160.) 


1. (Color reaction.)—Dissolve one drop of the alcohol in 3 cc. of water in a six-inch 
test-tube. Wind a piece of rather light copper wire around a lead-pencil so that the closely 
coiled spiral shall form a cylinder 2 cm. in length, while 20 cm. of the wire is left unbent 
to serve as a handle. Oxidize the spiral superficially by holding it in the upper part of 
the flame of a Bunsen burner; and then, while still at a red heat, plunge it into the alcoholic 
solution. (This treatment oxidizes a portion of the methyl alcohol to formic aldehyde.) 
Withdraw the spiral immediately and cool the test-tube with running water. Repeat 
the oxidation of the solution twice more by the method given. Add one or two drops 
of 0.5 per cent aqueous solution of resorcin. Pour the mixture slowly into a second 
inclined test-tube containing 3-5 cc. of pure concentrated sulphuric acid. The procedure 
and the phenomena in the test from this point on, are the same as described in the latter 
part of Test 114-1 for formic aldehyde. 

Many methyl ethers, and methyl esters that are sufficiently soluble in water to be 
tested by this method, and tertiary butyl alcohol, show the same behavior as methyl alcohol. 
Remember that the actual separation of bright-red solid flocks from the aqueous layer above 
the sulphuric acid, after standing, is essential to the proof that methyl alcohol is present. 

Many compounds besides those mentioned give traces of formic aldehyde when oxidized 
by a hot copper wire, but not enough to give a separation of the characteristic flocks. 
Test 114-2 for formic aldehyde will often show the presence of these traces, and there- 
fore must not be substituted for Test 114-1. Ethyl, propyl, isopropyl, butyl, isobutyl, 
hexyl, and allyl alcohols, ethyl ether, and acetone, give strong yellow, amber, ocher- 
ous, or dirty greenish colorations; and, if present in relatively large quantities In mixtures 
containing methyl alcohol, will interfere with its detection by destroying the purity of 
color required in the flocks. 

Weak aqueous solutions suspected to contain methyl alcohol may be oxidized directly 
with the copper wire and then tested with resorcin in the usual manner, solutions much 
weaker than the one recommended in the procedure giving entirely satisfactory results. 

In examining organic mixtures for methyl alcohol the precautions mentioned in the 
following paragraphs should be observed. 

(a) Use for the test only that part of any mixture that can be completely distilled 
between 50° and 100°, and which, after distillation, gives a clear, colorless solution when 
diluted with several volumes of water. 

(b) Make a blank experiment, before oxidation with the copper spiral, by pouring 
2 ce. of a clear aqueous distillate of the proper boiling-point, to which one drop of 0.5 per 
cent resorcin solution has been added, so as to form a layer upon concentrated sulphuric 
acid in a test-tube. If a precipitate or strongly colored ring makes its appearance, the 
solution is not suitable for testing without preliminary treatment. 

(ec) Do not test by this method any solution that is suspected to contain phenols 
or organic bases. 

2. Convert four drops of the alcohol into its 3, 5-dinitrobenzoate by the procedure 
detailed in the first paragraph of Test 814-1 for ethyl alcohol. 

Boil the reaction product with 12 cc. of dilute ethyl alcohol (3:1). Cool, shake, 
allow to stand for a minute or two, and filter. Wask with 2 cc. strong cold alcohol. 
Recrystallize from 12 cc. of boiling dilute alcohol (8:1). Cool, shake, and allow to stand 
for a minute or two, and filter. Wash the crystals with 2 cc. of cold strong alcohol. Dry 
at a temperature not above 100°, and determine the melting-point. 

The crystalline methyl dinitrobenzoate obtained in this test melts at 107.5° (uncor.). 


172 SPECIFIC TESTS FOR THE ALCOHOLS. 


820. Propyl Alcohol. (Properties tabulated on p. 161.) 


1. Oxidize four drops of the alcohol with six drops of the chromic-acid mixture used in 
Test 811 for allyl alcohol. The procedure for the oxidation is identical with that given 
for allyl alcohol, except that the aldehydic vapors are to be conducted into a three-inch 
test-tube containing a solution of 0.2 grm. -naphthol in a mixture of 2.0 ce. glacial acetic 
acid and two drops of concentrated hydrochloric acid. Warm the mixture for at least 
half a minute over a small flame, and then boil gently for one minute. Cool and shake. 
If no precipitate appears, add one drop of water and shake again. Continue the addition of 
water in this way until a scanty permanent solid precipitate is produced, and the mixture 
begins to show signs of becoming milky. Allow the precipitate to settle. Filter and 
wash with 2 cc. of dilute alcohol (1:1). Boil the precipitate 30 seconds with 3 ce. of 
strong alcohol and 1 cc. of water. Cool, shake, and filter. Wash with 2 cc. of alcohol 
(1:1). Press on a tile and dry 15 minutes at 100°. 

The condensation product formed in this test crystallizes in colorless plates, and 
melts at 153° (uncor.). 

2. Convert into propyl 3, 5-dinitrobenozate, following exactly the directions given 
in Test 819-2 for methyl alcohol, except that the product must be dried at a tempera- 
ture below 70°. 

The melting-point of propyl 3, 5-dinitrobenozate is 73°-73.5° (uncor.). 

821. Cholesterine. (Properties tabulated on p. 158.) 

So many compounds closely resembling cholesterine have been described that tests 
(1) and (2) should both be applied. 

1. Place 0.1 grm. of the compound and 0.5 cc. benzoyl chloride in a dry test-tube. 
Immerse the end of the test-tube in a paraffin bath and heat at about 160° for 5 minutes. 
Cool. Add 10 c.c. of strong alcohol and boil. Cool. Filter off the precipitate and wash 
it with 5 ec. of cold strong alcohol. Redissolve in 10 ce. of hot alcohol; cool; filter and 
wash as before. Then repeat these operations for a third time. Dry the product for 15 
minutes at 100° and determine its melting-point in a wide capillary. After the com- 
pound has fused to a perfectly clear liquid, withdraw the tube quickly from the 
bath, hold it before a piece of black paper, and watch closely for color changes during 
solidification. 

Cholesterine benzoate, formed in this test, crystallizes in pearly white leaflets which 
fuse to a turbid liquid at 145.5° (uncor.). At 178.5° (uncor.) the turbidity suddenly dis- 
appears. In cooling, a brilliant display of opalescent colors is exhibited, among which a 
brilliant blue, appearing at about the temperature of the higher melting-point, followed 
by a violet-blue just before complete solidification, are most prominent. The colors dis- 
appear very quickly. 

2. Place 0.1 grm. of the substance, 0.1 grm. of anhydrous sodium acetate, and 1 ce. 
of acetic anhydride in a dry test-tube. Immerse the end of the test-tube in a paraffin- 
bath at 130°-135° and heat for fifteen minutes. Dissolve the reaction product in 5 ce. 
of hot dilute alcohol (4:1). Cool. Filter. Wash the precipitate with 2 cc. of the same 
dilute alcohol. Recrystallize from 10 cc. of the same alcohol. Recrystallize again from 
3 ec. of boiling strong alcohol, and wash the precipitate with 1 cc. of cold strong alcohol. 
Dry on a porous tile, and then ‘in an oven at 100° for fifteen minutes. Determine the 
melting-point of the substance, and observe any change in color during solidification, in 
the manner described for the benzoate in the preceding paragraph. 

Cholesterine acetate, formed in this test, melts at 114° (uncor.). A play of opalescent 
color is observed during the few seconds that elapse between incipient and complete solidi- 
fication. 


CHAPTER XI 


GENUS IX. HYDROCARBONS AND OTHER COLORLESS 
COMPOUNDS OF CARBON, HYDROGEN, AND OXYGEN 
NOT INCLUDED IN EARLIER GENERA 


OF 


SUBORDER 1 ORDERSI: 


GENUS IX COMPRISES ALL COLORLESS COMPOUNDS OF THE SUBORDER THAT 
FAIL TO GIVE GENERIC TESTS I-VIII INCLUSIVE. WITH THE EXCEPTION OF 
SOME ETHERS AND A FEW UNREACTIVE KETONES AND ESTERS, THESE 
SPECIES ARE ALL HYDROCARBONS. ALL ARE INSOLUBLE OR NEARLY IN- 
SOLUBLE IN WATER. THE GENUS HAS NO SPECIAL GENERIC TEST OF ITS 
OWN. 

Tue solid species of the genus constituting Division A are not subdivided into 

sections. 7 

The liquid species, Division B, are, however, arranged in three sections: Sec- 
tion 1 contains the paraffins, C,,H,,,,, and some saturated cyclic hydrocarbons; 

Section 2, unsaturated hydrocarbons from both the aliphatic and cyclic series, 

together with some alky] oxides (ethers) ; and Section 3, the liquid aromatic 


hydrocarbons, terpenes, and a few fatty-aromatic ethers. 


SECTIONAL TESTS. 


To find the section of the tables to which any liquid species of the genus 
belongs, its specific gravity must first be known. Detailed directions for the deter- 
mination of this constant with the necessary degree of accuracy, by a simple metho: 
requiring not more than 0.2 cc. of substance, will be found on page 228. 

If the specific gravity at 20°/4° is found to be less than 0.850, the compound 
is to be sought in Section 1 or 2, Section 3 containing all liquid species having a 
higher gravity. In this case, in order to decide whether the body belongs to Section 
1 or 2, apply Tests 901 902. and 903. 

If a compound with specific gravity below 0.850 does not decolorize bromine 
solution in the cold in Test 901. and is not attacked or dissolved by the fuming 
sulphuric acid in Test 902, nor by the fuming nitric acid in Test 903, it is to be 
sought in Section 1.* If it shows the opposite behavior in any one of these tests, 
its place is among the unsaturated hydrocarbons and alkyl ethers of Section 2. 
TE ara ine ro come raaciive i Rien ta CHEM ner aria oe 


may be misplaced in Section 1. (Cf. Engler-Héfer’s “ Das Erddl,” 1, 231-5, for discussion.) 
: | 173 


a 


COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I] 


Melting-point 
(CS): 


22-5 


26-7 


30 
30 





GENUS 


IX, HYDROCARBONS, ETC. 


DIVISION A,—SOLID HYDROCARBONS. 


Boiling--point 
(Ox): 


274 


134 (15 mm.) 
270°5 


233 


236 (15 mm.) 
250 (th. i.) 


190-2 (13 mm.) 
155 (15 mm.) 


287-5 


179 (15 mm.) 
160 (15 mm.) 


233¢c, 


289 
303 
180 (15 mm.) 
261-2 
286 
230 (15 mm.) 
240 (15 mm.) 


317 
252-5 


294 


184 (15 mm.) 


HYDROCARBONS, ETC.—Colorless and Solid. 


Cetene, C,,H;,.—G. 0-789'°/,.—Gives Test 901. Dibromide an 
oil. 

Tetradecine(4), C,,H,,.—G. 0-800'*/,.—Gives Test 901. 

Pentadecane, C,;H,,.—G. 0-769?°/,—-Does not give Tests 901 
to 903. 

Safrol, C,,H,,0,.—Odor like sassafras, 
this genus. 

m-Methylhexadecylbenzene, Me.C,H,.C,,H,3.—G. 0-862!1/,. 

I, 2,4, 5-letraethylbenzene, C,H,.Et,.—Oxid. gives pyromellitic 
ac. 

Diphenylheptane, Ph,.CH.C,H,..—Nitrates easily. 

Hexadecine(1), C,,H39.—G. 0-797(20°).—Unsat. (Test 901). 
Gives floc. ppt. when shaken with AgNO, sol. 

Hexadecane, C,,H,,.—G. 0-775'8/,— Does not give Tests 901 
to 903. 

Octadecylene, C,,H,,.—G. 0-79118/,. 

Hexadecine(2), C,,H3).—G. 0-804?°/,. 
AgNO. 

} Anethol, Me.C,H,.C,H,.0.Me.—Has odor and taste of anise oil, 
in which it occurs!—G. 0-98557"/,; Np (18°) =1-5615.— 
V.d.s.aq.; misc. alc. or eth.—Shaken w. a little conc. H,SO, 
gives anisoin, m. p. 140°-5°.—Heated w. solid KOH at 
200°-30° gives p-oxybenzoic ac. and anol. 

Ditolylmethane, (Me.C,H,),.CH,.—Oxid. by CrO, to dimethyl- 
benzophenone, etc. 

Heptadecane, C,,H,,.—G. 0-7777*/,.Does not give Tests 901 
to 903. 

Octadecine(1), C,,H,,.—Gives cryst. ppt. w. ale. AgNO, sol. 
(C,,H,Ag.AgNOs). 

{ Diphenylmethane, Ph,.CH,.—G. 1-001°*/,.—Agreeable orange- 
like odor.—Oxid. by CrO, gives benzophenone (cf. Tests 
702 and 714).—See color reaction 904. 

Benzyl-p-tolyl-methane, Ph.CH,.CH,.C,H,.Me.—H. s. alc. 

Cetylbenzene, C,,H,,.Ph.—G. 0-8577'/,.—-D. s. c. ale.; e. s. eth. 
or bz. 

p-Methylhexadecylbenzene, Me.C,H,.C,,H,3;.—Test 905-3 gives 
p-toluic acid. 

Octadecane, C,,H;,.—G. 0-77778/,.— Does not give Tests 901-3. 

Phenyl Eth., Ph,.0.—Odor like geranium !—AIm. i. aq.; e. s. 
alc.—Unchanged by CrO, in Ac, by ignition w. Zn dust, or by 
HI at 200°.—Dissolves in fuming HNO,, giving dinitro- 
comp., m. p. 135°. 

{ Apiol, CH,.0,.C,H(C,H,).(OMe)..—I. aq.; e. s. alc. or eth_— 
S. H,SO, w. blood-red color.—Vol. w. st. 

Octadecine(2), C,,H;,.—G. 0-802°°/,—Gives no ppt. w. ale, 
AgNO, sol.—Gives Test 901. 


Cf, Div. B, Sec. 3, of 





No ppt. w. alc. sol. of 





174 


GENUS IX, DIV. A. 175 


(ORDER I, SUBORDER I.) 


————————————————————— ee SeeeSeeeeeeeseSeeeeeeeeeesSseFSSeFesSeee 


Melting-point 
Oey: 


32 
32-5 


32-9 


33-5 


35:5 


36 
36 


36-7 


36-7 
37 


38-9 


39 
40 
40-4 
41-2 


43. 


44-4 
47 
47 


47-7 
48-50 


50 
51-1 
51-2 


52 
52 


52 
53 


55 
55-6 
55-6 

57 


Boiling-point 
(C2): 


330c. 
241-2 (th. i.) 


170d. 


250 (15 mm.) 


350 


249 (15 mm.) 


300-3 


205 (15 mm.) 


274-5 
286-7 
258 


215 (15 mm.) 
241 


224-5 (15 mm.) 


235 
157c. 


234 (15 mm.) 


dist. 
243 (15 mm.) 
159 (th. i.) 


284 
255: 5c. 


230 


300 


HYDROCARBONS, ETC.—Colorless and Solid. 





ees Ci9H,).—G. 0-777°7/,.—Does not give Tests 901- 

03. 

-Methylnaphthalene, 
ane ee 1 Bhs 

Dicyclopentadiéne(1, 3), C,,H,,.—G. 0-977°3/,.—Lustrous stel- 
late aggregates, e. s. alc. or eth.—On dist. partially decom- 
poses to cyclopentadiéne (IX, B, 2), b. p. 42-5°. 

1, 3- Dimethyl-4-hexadecyl- benzene, Me,.C,H;.C,,H33.— G. 
0-84933/,. 

6-Benzylnaphthalene, C,H,.C,,H,,,—G. 1-176(0°).—CrO, oxid. 
to benzoic ac.(Test 312).—Picrate yellow ndl. fr. ale. w. m. p. 
93°. 

Octadecylbenzene, C,,H,;.Ph.—Silvery lft. 

&-Naphthylacetylene, C,,H;,.C‘ CH.—Ag salt, AgC,,H, (w. am- 
mon. AgNOQ,), colorless ppt. 

Benzoylmesitylene, C,H,.(Me,)(C;H;)(1, 3, 5, 6).—Lustrous ndl. 
—Tribrom-deriv. yellowish pr. fr. alc., m. p. 185°. 

Eicosane, C,,H,,.—G. 0-778°*''/,.—Does not give Tests 901-903. 

Ethyl 8-Naphthyl Eth., Et.O.Ci»H;—Odor anise-like!—Cryst. 
mass. 


Phenyl Benzyl Eth., Ph.O.C,H,.—Heated at 100° w. conc. HCl 
gives phenol and benzyl chloride. : 


1, 4-Diphenylbutene(1), Ph,.C,H,.—S. alc. or eth. 
I, 3, 5-lrimethyl-6-hexadecyl-benzene, Me,.C,H..C,,H;3. 
Heneicosane,C,,H,,.—G.0-778*°/,— Does not give Tests 901-903. 
Methylphenylfurfurane, Me.C,H,O.Ph.—Nadl. fr. c. alc.; e.s. ale. 
or eth.; i. aq.—Vol. w. st.—On long standing changes to 
yellow oil.—K. oxid. by alkaline KMnO, to benzoic ac.— 
Br gives brown-colored 1. lft., m. p. 208°-10°. 
Phloroglucin Triethyl Eth., C,H,.(OEt),.—I. aq.; v.s. alc. or 
eth.—Vol. w. st. 
Docosane, C,,.H,,.—G. 0-778**/,,— Does not give Tests 901-903. 
Pyrogallol Trimethyl Eth., C,H,.(0Me),.—E. s. alc. or eth. 
i-Camphene, C,,H,,.—Feathery ndl., v. s. alc. or eth.—Proper- 
ties like those of [+ or —] comp. of m. p. 51°-2°. 
Tricesane, C,,H,..—G. 0-778*""7/,.— Does not give Tests 901-903. 
9, 9-Diethylanthracene-g, 1o-dihydride, C,,H,,.—Easily oxid. by 
cold sol. of CrO, in glacial Ac to diethylanthrone, m. p. 136°. 
p-Cresyl Eth., (Me.C,H,),.0.—V. s. eth.; s. alc. 
Tetracosane,C,,H,,.—G.0-779°'/,.— Does not give Tests 901-903. 
[+ or —]Camphene, C,,H,,.—(In many essential oils like citro- 
nella oil.)—Feathery cryst. fr. alc.; v. slowly attacked by 
cone. H,SO,.—Gives Test 901; is attacked in Test 905. 
—The hydrochloride (C,,H,,.HCl) is solid but unstable. 
Dibenzyl, Ph.CH,.CH,.Ph.—G. 0-995.—Mod. s. c. alc.; e. s. eth. 
Phloroglucin Trimethyl Eth., C,H;.(OMe),(1, 3,5).—S in cone. 
HNO, w. deep-blue color! EK. s. ale. or eth. 
s-Diphenylbutane, Ph.(CH,),.Ph.—E. s. alc. or eth. 
Pentamethylbenzene, Me,.C,H.—W. conc. H,SO, gives hexa- 
methylbenzene, m. p. 164°. 
Cetyl Eth., (C,,H;,)..0.—Lit. 
Phenyl-ditolyl-methane, Ph.CH.(C;H,),.—Ndl s alc; v s. bz. 
Dimethyl Hydroquinonyl Eth., p-C,H,.(OMe),. 
Isobutylanthracene, C,,H,,.—Fluorescent ndl.—Reddish-brown 
picrate. 


Me.C,,H;.—Picrate dark-yellow ndl., 





176 


Melting-point 
(Coy 





57-8 
58 
59 


59 
59-5 
59-5 

60 
60°5 
60-1 

62 


62 
63 
63 
63-4 
64 
67 


68-1 
69 


70 
70-5 


70-5 


Boiling-point 
(C.2). 


350 
354 
270 (15 mm.) 
275-300 
310 
a. 360 


370-80 
290 


440 
129-30 


302 (15 mm.) 


231-6 
254: 6c. 


310(th.i.15mm.) 


a. 360 


274 


331 (15 mm.) 


abt. 190 


218-2 


GENUS IX, DIV. A. 


(ORDER I, SUBORDER I.) 





HYDROCARBONS, ETC.—Colorless and Solid. 





Cerotene, C,;H,,.—Gives Test 901.— Paraffin-like mass fr. 
Chinese wax. 

+ Dinonyl Ketone, (C,H,,),.CO.—Description w. Ketones. Cf. 
ViILVAP pass. 

g-Isoamylanthracene, C,g.H».—Alc. sol. shows bluish fluores- 
cence.—Picrate forms brown-red ndl. fr. ale., w. m. p. 115°. 
—Sol. in conc. H,SQ, is green, becoming red on warming. 

a-Benzylnaphthalene, PhCH,.C,,H,;.—S. in 30 pt. h. alc.; s. in 
2 pt. eth.—Picrate forms yellow ndl., w. m. p. 100°-1°, 

Diphenyl-o-tolyl-methane, Ph,.CH.C,H,.Me.—D. s. c. alc.—May 
be characterized by conversion into rosaniline, 

Heptacosane, C,;H,,.—G. 0-780°*°/,—Does not give Tests 
901-903. , 

Tolane, PhC:CPh.—Lft. s. alc—CHCl, sol. saturated w. Cl 
gives tetrachloride, m. p. 163°; s. in h. bz.—Gives Test 901. 

Benzylduryl, PhCH,.C,H.Me,(Me, =1, 2, 4,5).—D.s. alc. or eth. 

Ethylanthracene, C,,H,Et.—Lft. s. ale.—Picrate melts at 120°. 

m-Methyl-triphenylmethane, Ph,.CH.C,H,.Me.—Nadl. v. s. ale.— 
No picrate.—Shows blue phosphorescence on friction, 

Melene, C;,H,,.—Cryst. s. h. alc. 

Anthracenehexahydride, C,,H,,.—Lft. v_ s. alc. 

2,5-Dimethyl-3, 4-Diacetylfurane, C,,H,,0,—Cf. VII, A. 

Anthemene, C,,H,,.—G. 0-942(15°).—V. d. s. c. ale.; s. eth. 

Hexadiene(1,4), C,H,,.—G. 0-739(0°).—Gives Test 901. 

Asarone, (MeO),.C,H,.C,H,.Me.—(In root of Asarum Europzeum.) 
—S. h. aq.; e. s. alc. or eth. 

Hentriacontane, C;,H,,.—G. 0-78°°/,.—Does not give Tests 901- 
903. 

Laurone, (C,,H,;),.CO.—Description w. Ketones. Cf. VII, A, 
p. 137. 

tert.-Dibutylbenzene, C,H,.[C.Me,],. 

{ Diphenyl, Ph.Ph.—G. 1-165.—S. in 10 pt. c. ale.—p-Brom- 
derivative prepared by action of Br in cold C8, sol.; m. p. 
310°.—Test 904 gives an intense and quite permanent blue 
(B) color! 

Dotriacontane, C,,H,,.—Alm. i. c. ale.; s. h. eth.; v.s. h. gla- 
cial Ac.—Does not give Tests 901-903. 

p-Diphenyl-tolyl-methane, Ph,.CH.C,H,.Me.—Pr. v. s. h. ale. 

2,4-(2)-Dimethylanthracene, C,,H,.Me,.—Ndl. fr. ale-—CrO, in 
Ac. sol. oxid. to dimethylanthraquinone having m. p. 157°-8°. 

Methyl a-Naphthyl Eth. (Nerolin), Me.0.C,.H;.—Odor like oil 
of neroli (Orange blossoms.)—Lft fr. eth.; d.s. ale. 

Pentatriacontane, C,,H,,.—G. 0-782'*"/,—Does not give Tests 
901-903. 

} Myristone, (C,,;H,7)..CO.—Description w. Ketones, VII, A, 
p. 138. 

-Dibenzylbenzene, (C,H,),.C,H,.— Flat ndl., s. ale-—Does not 
give a picrate. 

af-Dinaphthyl, (C,,H;),.—S. ale.—Picrate forms golden ndl., 
m. p. 155°-6°. 

Durene, C,H,.Me,, (Me, =1, 2,4,5).-—V.s ale.—Odor like cam- 
phor.—Sbl 

{ Naphthalene, C,,H,.—G. 1-152(15°).—Lft., s ¢. ale.—Char- 
acteristic odor.—Test 904 w. AICI, gives a green-blue color !— 
Br substitutes very easily —Oxid. w. KMnO, (Test 905-1) 
gives o-phthalic acid (yield small).—Identify by Test 915! 


GENUS IX, DIV. A. 177 


(ORDER I, SUBORDER I.) 


= 





ie erst HYDROCARBONS, ETC.—Colorless and Solid. 








82-8 Bee tes (C,;Hs;,)2.CO.—Description w. Ketones, VI{, A, on 
p. ‘ 


83-4 Isopropylstilbene, C,H,.C,H,.C,H,.Ph.—Scales, v. s. h. ale.— 
Adds Br, (Test 901). 
85 285(100 mm.) | p-Benzyl-diphenyl, C,;H,.C,H,.Ph.—Lft. s. alc—Heated w. 
H,SO, evolves SO, and finally gives intense blue-red color.— 
Does not give a picrate.—Oxidation gives benzophenone 
(Test 714). 
86 a-Dibenzylbenzene, (C,H,),.C,H,— Flat ndl., v. s. h. alc.—No 
picrate. 
86-7 287-8 (th. i.) | Biphenylene Oxide, C,.H,0.—Small lft. fr. alc.; v.s. eth.; 1. 
aq.—Picrate fr. alc. m. p. 94°.—Sol. in CS, gives with Br, 
a cryst. dibrom-deriv., m. p. 185°, d.s. alc. 


87-8 + Stearone, (C,,H,,),.CO.—Description w. Ketones, VII, A, p. 
138. 


88 270 Perhydroanthracene, C,,H,,.—Completely oxid. by CrO, (cf. 
Test 905-2).—Scarcely attacked by Br. 

88 Diphenyl-diacetylene, PhC:C.C:CPh.—Long ndl., e.s ale.— 
Picrate light yellow rhombic cryst. fr. ale., m. p. 108°.— 
Adds Br (cf. Test 901).—Carbonized by h. conc. H,SO,.— 
Gives no ppt. w. ammon. AgNO, or CuCl. 

88-9 a. 360 Benzyl-pentaethyl-benzene, C,H;.C,.Et,.—100 pt. alc. at 18° 
dissolve 0-9 pt. 

89-90 Ethylstilbene, p-Ph.C,H,.C,H,.Et.—Lft. v. s. h. ale-—Unsat. (cf. 
Test 901) 

91 343-5 Diphenylfurfurane, C,,H,,0.—E. s. alc. or eth.—S. cone, H,SO, 
w. green color! 

92 358-9 + Triphenylmethane, Ph;.CH.—Lft. d. s. ¢., e. s. h. alc.; e. 8. 
eth. or CHCl,.—t Nitrate 0-1 grm. by dissolving in 2 cc. 
fuming HNO, without application of heat. Ppt. the yel- 
lowish trinitro-compound by diluting w. aq. Dissolve the 

pt. in 10 cc. hot glacial acetic ac. and reduce by successive 
additions of small portions of Zn dust to the hot sol., until 
the strong red color that at first appears is nearly discharged. 
Decant, and add a few cgrm. PbO, to the solution, A very 
intense fuchsine-red color (pararosaniline) forms at once.— 
For color reaction w. AICI, see Test 904. 

92 B-Dinaphthylmethane, (C,,H;)..CH,—M. p. of dibrom-deriv- 
ative 164°. 

92-5 a. 360 Phenyl-di-p-xylyl-methane, Ph.CH.(C,H,Me,),.—E s. alc.—Sols. 
show bluish fluorescence. 
92-3 265-75d. Acenaphthylene, C,,H,.—Golden yellow tbl. v. s, alc.—Picrate 
: forms yellow ndl., v. d.s. c. alc.; m. p. 201°-2°. 


94 323 Dicamphenehydride, CxH,,.—Very stable.—Little attacked by 
CrO, mixture. 
95 277°5 + Acenaphthene, C,,H,o.—Long ndl fr alc.—D. s. ¢. alc.; e. s. 
h. ale.—Identify by Test 911! 
96-5-7 Retenefluorene, C,;H,,.—S. in alc. w. violet fluorescence.—Com- 


pletely destroyed by CrO, in Ac sol.—HNO,, G. 1-43, gives 
a dinitro-compound, d s alc., m. p. 245°. 

98-5 390 Retene, C,,H,,—_G 1-13'%/,,.—Micaceous lft.—V. s. h. ale.— 
Picrate forms orange ndL, m. p. 123°-4°. — Dibrom-com- 
pound, fr. Br+aq., tbl. fr. CS,, m. p. 180°; alm. i. aq. 


98-5 Ethylene Diphenyl Eth., C,H,.(OPh),.—D. s. c. aq.; e. 8. h. aq. 
or eth. 
100 340 (th. i.) + Phenanthrene, C,,H,,.—Sbl easily.—Lit., s. in 10 pt. h. ale.— 
Identify by Test 916! 
100-5 | 315¢. Xanthene, C,;H,,0.—Lft fr. alc.; alm. i. aq.; s. eth., s. conc. 


H,S0, w. yellow color and green fluorescence. 


178 


GENUS IX, DIV. A. 


(ORDER I, SUBORDER I.) 





Melting-point 
(Greys 
102 
102-2:-5 
105 
105 
105-6 
108-5 


109 
109-10 


110 


se 


112-13 


113 
116 
116-17 
117-20 


119 
120-0-5 


121 
123-5 
124 
124 


125 
126-7 


128 


128 
128 
129 


Boiling-point 
(GED. 


345c¢. 
a. 360 
290-300 
dist. 
313 


a. 360 
217 (30 mm ) 


dist. 


315 


295 (th. 1.) 


295 


dist. 


dist. 


dist. 


306-7 (th. i.) 


292 


298c. 


HYDROCARBONS, ETC.—Colorless and Solid. 





Benzylfluorene, C,H,.C,,Hp). : 

$-Phenylnaphthalene, Ph.C,,H,.—Lft., e. s. h. ale-—Cryst. show 
blue fluorescence.—Vol. w. st. 

$-Naphthyl Eth., (C,,H,),.0.—E. s. h. alc.; v. s. eth.—Picrate, 
orange lft. fr. warm eth., m. p. 122°. 

Sequoiene, C,,H,,.—(In needles of Californian Sequoia gigantea.) 
—Odorless lft. w. faint bluish fluorescence.—Red picrate. 
Tetramethyl-m-stilbene, Me,.C,H,.C,H,.C,H;.Me,.—S. h. ale.— 

Adds Br, (cf. Test 901). 

Anthracenedihydride, C,,H,,.—Sbl. in ndl—Warmed w. conc. 
H,SO, gives SO, and anthracene (Test 912). 

a-Dinaphthylmethane, (C,,H,),.CH,.—S. in 15 pt. h., or 120 pt. 
c. alc.—Picrate (fr. h. CHCl; sol.) red-yellow ndl., m. p. 
142°-3°, 

Fluoranthene, C,;H,,.—Cryst. d. s. c. ale-——Equal parts of 
picric ac. and hydrocarbon in h. alc. give a stable picrate; 
long orange ndl, m. p. 182°-3°! 

a-Naphthyl Eth., (C,,H;),.0.—E. s. h. ale.; s. eth.—Picrate, 
m. p. 115°.—Sols. show pale bluish fluorescence. 

Benzhydrol Eth., Ph,C,O.—Monoclinic cryst. fr. bz.; d.s. h. 
ale.—Boiled w. glacial Ac, Zn, and a little HCl gives tetra- 
phenyl ethane. 

Fluorene, C,;H,,.—Lft. d.s. c. ale—Unstable red-brown picrate 
fr. eth. sol., m. p. 79°-80°.—Diphenylene ketone is formed 
by oxid. w. CrO,; mixture. The ketone may be dist. w. 
steam, slowly cryst. fr. alc., and mechanically separated 
from the unoxid. hydrocarbon (A, 166, 368). 

Dibenzyl-biphenyl, C,,H,.(C,;H,)..—Lft., s. ale. 

y-Methylenebiphenyl, C,,H,,.—S. h. alc. w. pale-blue fluores- 
cence.—Picrate forms blood-red ndl., m. p. 79°-81°.—CrO, 
mixture gives a quinone. 

Di-o-Oxyhydrobenzoin-Diésoanhydride, C,,H,,0,.—Ndl. fr. alc.; 
e. s. ale. or eth.—Not attacked by h. dil. HCl or NaOH. 

Phenyl-p-tolylethylene, Ph.CH: CH.(C,H,.Me)(1: 4).— Pearly lft., 
d. s. ale.—M. p. dibromide 186°-7°. 

Methyl-phenyl-anthracene, Me.C,,H,.Ph.—Yellowish cryst.— 
Dil. alc. sol. shows strong green-blue fluorescence-—CrO, 
oxid. to methyl-pheny]-oxanthranol, 

Phenylanthracenedihydride, C,,H,,.—Hot alc. sol. shows blue 
fluorescence.—Brown-red picrate.—Oxid. by CrO; to phenyl- 
oxanthranol. 

p-Ditolyl, C;H,.C;H,;— Glassy pr. fr. eth. 

Dimethyl-diphenyl-ethane, Me.CHPh.MeCH.Ph. 

Distyrene, (C,H,),.—Tbl. 

{ Stilbene, Ph.CH:CH.Ph.—Tbl., d. s. ale-——Adds Br, hot.— 
Warmed w. CrO, mixture gives benzaldehyde (Test 113) 
and benzoic ac. (Test 312). 

Di-p-xylyl, (C,H;.Me,),. 

Hydrobenzoin Anhyd., C,.]H,,0,.—Cryst. fr. eth., i. aq.; e. s. h, 
alc.—Heated at 250°-70° gives benzaldehyde and stilbene.— — 
Not vol. w. st. 

Diphenylene-tolyl-methane, C,,H,.CH.C;H,.—Silky ndl—Gives 
no picrate. 

tert-Tributylbenzene, C,H,.(CMe,)3;.—Scales fr. alc. 

Methyl-ethyl-diphenyl-methane, (Me)(Et).C.Ph,. 

Hexaethylbenzene, C,Et,.— May be cryst. fr. warm fuming H,SO,. 





GENUS IX, DIV. A. 179 


(ORDER I, SUBORDER I.) 





Melting-point 
(CS). 





131 
132 


133-5-4-5 
134-5 
136 


141 
140-5 
145 
145-5 
148 
148-9 
148-5 


149 
152-3 


154 
155-6 
157 
160 
161 
161 


161 


162 


164 
169-70 


171 


171-1-5 


Boiling-point 
CONS): 


355 (12 mm.) 


326 
a. 360 


250 


much a. 360 


417 


a. 360 


dist. 


dist. 


360 


264 


dist. 


HYDROCARBONS, ETC.—Colorless and Solid. 


Dibenzylmesitylene, (C,;H,)..C,H.Me,.—Cryst., v. d. s. alc. 
Metanethol, (C,,H,,0)z.—Sbl. at 115°-20°.—Not vol. w. st.— 
Ndl. fr. eth., d. s. c. ale-—Oxid. by CrO, gives acetic acid. 
Isoanthracene, C,,H,,.—Pearly Ift., d. s. c. ale-—CrO, in Ac sol. 

oxid. to a quinone w. m. p, 211°-12°. 

p-Diethylstilbene, (Et.C,H,),.C,H,.—Pearly lIft., d. s. ¢. ale.— 
Oxid. gives terephthalic ac. (Tests 905 and 318-3.) 

1, 1-a-Dinaphthylethane, (C,,H,),.CH.CH;.—Lft.—Solutions flu- 
oresce violet.—S. c. ale. 

Naphthanthracene, C,,H,,.—Sbl. in lft—Shows intense yellow- 
ish-green fluorescence.—Forms a red picrate, ndl. fr. bz., 
Di pwlooy 

Anisoin, (C,,H,,0)z.—(Not identical with compound bearing 
same name in Genus VII.)—Small ndl. fr. eth.—Dec. on 
dist. to liq. metanethol.—Not attacked by dil. ac. or alk. 

Benzylduryl, C,H,.C,H.Me,.—D. s. alc. 

Biphenylene-phenyl-methane, C,,H).Ph.—Ndl. d_s. ale.—No 
picrate.—With Br in h. Ac sol. gives dibromide, m. p. 181°-2°. 

1, 4-Diphenylbutadiéne(1, 3),C,,H,,.—Pearly tbl—Tetrabromide 
melts at 230° d. 

Pyrene (Phenylenenaphthalene), C,,H,,.—Tbl. s. h. ale.—Pic- 
rate, stable red ndl. fr. alc. sol. v. d. s. c. ale., m.p. 222°. 

Phenylene-diphenyl-methane, C,H,.C.Ph,.—Oxid by CrO, mix- 
ture to benzophenone (Test 714) and benzoic ac (Test 312). 

1, 1-Dinaphthylethylene, (C,,H,),.C,H,.—Silky ndl. sh. ale. 

Phenylanthracene, Ph.C,,H,.—Lft. s. h. ale——Solutions show 
blue fluorescence.—Gives red cryst. picrate. 

aa-Binaphthyl, (C,,H,),.—Tbl. s. ale—Unstable red-brown 
picrate fr. bz., m. p. 145°, decomposes in air. 

Benzylphenanthrene, C,,H,,.—V. d. s. ale——Oxid. by CrO, in 
Ac sol. to phenanthrenequinone (Test 1013) and benzoic ac. 
(Test 312). 


Tetramethyl-p-stilbene, (Me,.C,H,),.C,H,.—Lft. d. s. h. ale 


1, 2-a-Dinaphthylethane, (C,,H,),.(CH,),,—Greenish-yellow §6- 
sided tbl.; d.s. ale. w. green-blue fluorescence. 

Hexamethylstilbene, (Me,.C,H.),.C,H,.—S. alc.—Picrate garnet 
cryst. fr. bz., m. p. 123°.—Adds Bry. 

a-Dinaphthostilbene, (C,,H,),.C,H,.—D. s. ale. or eth.; e. s. bz. 
—CrO, gives a-naphthoic ac. 

2, 6(@)-Dinaphthylene Oxide, C,,H,,0.—Silvery Ift., d.s. h. ale.; 
e. s. eth.; s. conc. H,SO, w. red color (dif. fr. a), which 
changes to violet and dark blue on heating, and on dilution 
Ww. aq. gives an orange-red fluorescent sol.!—Picrate ver- 
milion ndl., m. p. 135°. 

Bi-phenylphenyiene-methane, (Ph.C,H,)..CH,.—V. d. s. ale.— 
S. w. blue color in conc. H,SO,.—Gives no picrate.—CrO, 
oxid. to a ketone. ; 

Hexamethylbenzene, C,Me,.—V. d. s. tbl. fr. ale —Sbl. in Ift.— 
Picrate, yellow rectangular tbl., m. p. 170° (dec. by alc.). 
s-Triphenylbenzene, Ph,.C,H;.—G. 1-206.—D. s. ale.—Oxid. by 
CrO, in Ac sol. to benzoic ac. (Test 312).—Br comp. fr. sol. 

in CS,, m. p. 104°. 

Tri-p-tolylbenzene, (C;H,);.C,H;—Alm. i. c. alc.; cryst. fr. 
CHCl,. 

s-Tetramethylanthracenehydride, C,,H,,.—Alm. i. alc.; tbl. fr. 
bz.—Oxid. by CrO, in Ac sol. to dimethylanthraquinone, 
m. p. 236°.—Picrate red-brown ndl., m. p. 165°. ot 


180 


GENUS IX, DIV. A. 


(ORDER I, SUBORDER I.) 





Melting-point 
(Cy: 





173-4 


173 
175 


176-4 
179 
181-1-5 
184 
187 
187-8 
188 
189 


196 
199-200 


199-200 
203 


204-5 


205 
207 


209 


216: 5c. 


215 
221 


222 
227 


231-2 
243 
244-5 





Ciara ck HYDROCARBONS, ETC.—Colorless and Solid. 
dist. 350-1 t+ o-Benzophenone Oxide (Xanthone), C,,H,O,.—Long ndl. fr. 


alc., i. c. aq.; s. h. alc.; d.s. eth.; s. conc. H,SO, w. yellow 
color and intense light-blue fluorescence !—(Does not react 
w. phenylhydrazine or hydroxylamine.)—Fusion w KOH 
gives salicylic acid and phenol !—CrO, mixture oxid, to CQ). 

Phthalacene, C,,H,,.—D. s. h. ale.-—W. an equal weight of Br in 
Ac sol. gives brom-derivative w. m. p. 184°. 

Tetraphenylfurane (Lepidene), Ph,.C,O.—Scales, i. aq.; s. 170 
pt. h. ale., 52 pt. c. eth., or 85 pt. c. bz.—Dibrom-derivative 
(by heating Ac sol. w. Br), lft., m. p. 190°. 

{ Camphor, C,,H,,0.—B. p. 205-3°.—Description w. Ketones, 
VI, A, p. 139, and Test 715. 

304-5 p.-Dimethylstilbene, (Me.C,H,)..C,H,.—Lft. d. s. h. ale-—Oxid. 

by CrO, (Test 905-2) gives terephthalic ac. (Test 318-3). 

9, 10-Dimethylanthracenehydride, C,,H,,.Me,.— Yellow ndl., s. 
ale.—Oxid. by CrO, in Ac to anthraquinone (Test 1011). 
a-Dinaphthylene Oxide, C,,H,,0.—I. aq. or alkalies; d.s. alc.; 

e. s. eth.—Picrate, dark-red ndl., e. s. ale. or bz., m. p. 173°. 
£@-Binaphthyl, (C,,H;),—D. s. ale.—Picrate orange ndl., m. p. 
184°-5° (B. 20, 662). 
a. 360 Dibiphenylene-ethylene, (C,,H,)..C,.— Yellowish-red ndl. — 
Heated w. Zn dust gives fluorene.—The picrate forms un- 
stable red-brown ndl. fr. alc. 


Tri-p-xylylmethane, CH.(C,H;,Me,),.—Grains, s. alc. 


Benzal-{-dinaphthyl Oxide, C;H,.C,,H,,0.—D. s. alc. or eth.; i. alkalies. 

Isochrysene, C,,H,,.—Long ndl.—Gives no picrate. 

a-Methylanthracene, C,,H,.Me.—Gives unstable red picrate-—Oxid. by CrO, te 
1-methylanthraquinone. 

$-Methylanthracene, C,,H,.Me.—Gives unstable red picrate-—Oxid. by CrO, in 
h. Ac to anthraquinonecarbonic ac. 

Isomethylanthracene, C,,H,.Me.—Oxid. by CrO, in Ac gives 7-anthraquinone- 
carbonic ac. . 

a-Benzpinacoline, C,,H,,0.—Stable at 350°.—Alm. i. ¢. ale.; e. s. bz. or CS,.— 
Does not react w. KOH or phenylhydrazine.—CrO, oxid. gives benzophenone 
(cf. Tests 905-2 and 714). 

p-Diphenylbenzene, Ph,.C,H,.—B. p. 383°.—Lft., v. d. s. h. ale.— Gives na 
picrate.—Oxid. by CrO, to terephthalic ac. (Tests 905-2 and 318-3). 


Photoanethol, C,,H,,O.—(Fr. anethol in sunlight.)—Odorless, tasteless, pearly 
Ift.—Sbl.—D. s. ale.; v. d. s. eth. 


s-Tetraphenylethane, Ph,.CH.CH.Ph,.—B. p. 379°-83° c.—Ndl. fr. CHCl,.—G. 
1-182.—D. s. h. ale.—Gives no picrate.—CrQO, oxid. to benzophenone (Test 
714). 

+ Anthracene, C,,H,,.—B. p. 351°.—Lft. or tbl., usually yellowish, but when per- 
fectly pure, colorless w. beautiful violet fluorescence.—D. s. h. ale.—Gives & 
deep-red unstable picrate (fr. bz. sol.), e. s. bz., and melting at 138°— 
Identify by Test 912! 

Tetratolylethylene, (C,H,),.C,. 

} Tetraphenylethylene, Ph,.C,—B_ p. 415°-25°.—V. d.s. ale.; e. s. bz.—CrO, 
in Ac sol. gives benzophenone (Test 714).—f Fails to give Test 901 for unsat- 
uration, and is not acted upon by alkaline permanganate in Test 304. 

I, 3, 6-Trimethylanthracene, C,,H,.Me;.—D. s. alc. 

I, 4, 6-Trimethylanthracene, C,,H,.Me,.—D. s. alc. —CrO, in Ac sol. gives tri- 
methylanthraquinone. 

Dimethylanthracene, C,,H,.Me,.—CrO, in Ac oxid. to a quinone w. m. p. 161°-2°, 

I, 2, 4-Trimethylanthracene, Me,.C,,H;. 

Tetraxylylethylene, (Me,.C,H,),.C,.— Yellowish lft. 





Se a ee ; = 


GENUS IX, DIV. A, 18] 


(ORDER I, SUBORDER I.) 





Melting-point 
(Ore). 


246 
250 


253 
254-5 


268 


abt. 280d. 


300 
307-8 


315 


364c. 


a, 360 


HYDROCARBONS, ETC.—Colorless and Solid. 


— 


2, 3-Dimethylanthracene, Me..C,,H,.—Lft. w. blue-green fluorescence. 

Chrysene, C,,H,,.—Scales w. red-violet fluorescence.—V. d. s. h. alc.; V. d.s. 
eth. or CS,.—The picrate fr. bz. sol. of components cryst. in long red ndl., m. 
p. 273°; it is not stable in alc. sol.—CrO, oxid. to chrysoquinone, which dis- 
solves in conc. H,SO, w. deep-blue color. 

1, 2-(@)-Dinaphthylethane, (C,,H,)..C,H,—Pearly tbl., d. s. h. ale.—Solutions 
fluoresce blue-violet. 

Hydroxylepidene, C,.H,.0,.—S. 100 pt. h. glacial Ac; s. after long boiling in alc., 
then melting at 260°-1°; i. eth. or alkalies.—Said not to give a phenylhydra- 
zone or oxime. (Position in classification open to question.)—W. conc. 
HCl at 130°-40° gives lepidene. 

Carbopetrocene, C,,H,.—Lft. or ndl. i. c. alc. or eth.; s. CS, or h. bz.—Gives 
orange-colored picrates. 

Tetramethylanthracene, C,,H,,. 

Bianthranyl, C,.H,,.—Lft. fr. toluene.—Convert into dinitro-compound, m. p. 
337° d. (B. 20, 2433). 

Benzerythrene, C,,H,,(?).—Lft. fr. bz—Alm. i. ale.; v. d. s. c. bz.—Dissolves 
w. green color in conc. H,SO,. 

Tetraphenylethylene Dioxide, C,,H,,0,.—Sbl.—Ndl. fr. bz., 1. ale.; s. cone. 
H,SO, w. yellow color.—Adds Br,.—Boiled w. dil. HNO, gives xanthone.~ 
Sols. show bluish-green fluorescence. 

Picené, C,,0,,.—B. p. 518°-20°.— Colorless lft. w. blue fluorescence.—D. s. h. bz. 
or CHCl,; s. conc. H,SO, w. green color.—Oxid. by CrQO, in Ac sol. to a 
quinone. Sol. in CHCl, gives with Bra comp.,m p. 294°, 


Truxene, C,,H,,.—TDbl. fr. h. xylene.—Alm. i. most solvents.—CrO, mixture gives 
a deep yellow i. quinone. 





COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I}. 
GENUS IX, HYDROCARBONS. 


DIVISION B, SECTION 1,—LIQUID HYDROCARBONS WITH SPECIFIC 
GRAVITY LESS THAN 0-85 AT 20°/4° THAT DO NOT GIVE 
TESTS 901 TO 903 IN THE COLD. 


Boiling-point 
(C.°). 





—153 
— 86 
—38-9 
abt. 0 
+1 
9-5 
31 
AY 
39-42 
49-7 
50-1 


86-7 
90-3c. 
91 
94 
95-8 
98-4 
101-2 


108 
118-9 


118 (th. i.) 
120-5-21 


ea lee) i=) 


oS 


Cro oo oo > 


O- 
O- 


O- 


O- 


Specific 
Gravity. 


-446(0) 
-535(0) 
-603(0) 
-60(0) 


-6281°7/, 
-634(15) 


-64979/, 
-751205/, 


668(17-5) 


-677(0) 


6772-5 /, 


-658(20- 9) 


¢ 75071/, 


-790°/, 


-711(0) 
-682(17-5) 
-690(20) 
-75420/, 
-689(27) 
-689(14-9) 
-769(2°/,) 


711"/, 
759(7°/o) 


809(20) 
769(7°/,) 


HYDROCARBONS.—Colorless Liquids with Specific Gravity less 
than 0-85 at 20°/4° that do not give Tests 901 to 903. 


Methane, CH,. 


Ethane, C.H,. 

Propane, Me.CH,.Me. 

Trimethylmethane, Me,.CH. 

Butane, C,H,,.—S. in 18 vol. c. ale. 
Tetramethylmethane, Me,.C.—M. p. —20°. 
2-Methylbutane, Me,.CH.CH,.Me. 

Pentane, C,H). 

Methylcyclobutane, Me.C,H,.—Does not add HI cold. 
Trimethyl-ethyl-methane, Me,.C.Et. 


Cyclopentane, C,H,,.—Br substitutes, but only at a high tem- 
perature.—Oxid. by HNO, gives glutaric ac., etc. 


Diisopropyl, Me,.CH.CH.Me,. 
2-Methylpentane, Me.(CH,),.CH.Me,. 
Methyldiethylmethane, Me.(Et,).CH. 


{+ Hexane, C,H,,. jt No evidence whatever of chem. action in 
Tests 901-903. 


Methylcyclopentane, Me.C,H,.—Not easily attacked by warm 
HNO,+H,SO,.—Fuming HNO, oxid. to formic, acetic, and 
glutaric acids. ; 


Cyclohexane (Hexanaphthene), C,H,,.—M. p. 4-7°.—‘‘ Not at- 
tacked by cold mixture of equal vol. conc. H,SO, and 
fuming HNO,.” ‘‘ Attacked by Br at 100°-110°.” 


Dimethyldiethylmethane, Me,.C.Et,. 

2-Methylhexane, Me,.CH.(CH,),.Me. 

3-Methylhexane, Me.CH(Et).(CH,),.Me. 

1, 3-Dimethylcyclopentane, Me,.C,H,. 

Triethylmethane, Et,.CH. 

Heptane, C,H,,. 

Hexahydrotoluene (Heptanaphthene), Me.C,H,,.—‘‘Not at- 


tacked by c. nitro-sulphuric” ac. W. Br and AIBr; gives 
pentabromtoluene, m. p. 282°. 
2, 5-Dimethylhexane, Me,.CH.CH,.CH,.CH.Me.. 
Hexahydro-m-xylene (Octonaphthene), Me,.C,H,,.—Cf. p. 186, 
Section 2. 


Cycloheptane, C,H,,.—Heated w. Br in sealed tube gives pentae 
bromtoluene. 


Hexahydro-p-xylene, Me,.C,H,).—Cf. p. 186, Section 2. 





182 


EEE 


GENUS IX, DIV. B, SECT. 1. 183 


(ORDER I, SUBORDER I.) 





Boiling-point Specific HY DROCAR BONS.—Colorless Liquids with Specific Gravity less 
(C.°). Gravity. than 0-85 at 20°/4° that do not give Tests 901 to 903. 
124 Methylethylcyclopentane, Me.C,H,.Et. 
125-5c. 0-719°/, } Octane, C,H,,. {No evidence whatever of chem. action in 


Tests 901-903 ! 
129-5-31-5 0-725(24-7) | B-Nonane, C,H. 





135-6 0-767(?°/,.) | Hexahydropseudocumene (Nonaphthene), Me,.C,H,(1, 3, 4). 
135-8 Mesitylenehexahydride, Me,.C,H,(1, 3, 5)- 
135-7 0-742(12-4) | a-Nonane, C,H.. 
147-50 0-787(20) Hexahydrocumene, Pr.C,H,,. 
149-7c. 0-7187°/, Nonane, C,H».—M. p. —51°. 
159-5 0-736°°8/, + 2, 7-Dimethyloctane, Me,.CH(CH,),.CH.Me,.—S. in 12 pt. c. 
glacial Ac. 
159-62 0-746(22) 3, 6-Dimethyloctane, Et.CHMe.(CH,),..CH(Me)Et.—Opt. active. 
160-62 0-783 (18) Dekanaphthene, C,H». (Fr. petroleum.) 
160-62 0-7887°/, a-Terpenetetrahydride, C,,H,,.—‘‘ Not attacked by conc. H,SO,. 
With fuming H,SO, heat is evolved, but the hydrocarbon is 
apparently not changed.” 
164 0-793*/, f-Terpenetetrahydride, C,,H».—‘‘Br substitutes when hot.— 
Nitro-sulphuric ac. gives no cryst. nitro product.” 
abt. 170 0-80(15) Hexahydro-p-cymene (‘‘ Terpane,” “‘ Terpilenehydride ””), C, ,H.p. 
—‘"Is not attacked by cold fuming HNO,, fuming H,SO,, 
or Br, 
173¢. 0-730(20) Decane, C,,H...—M. p. —30°-32°. 
173-80 0-837(1°/,) | Naphthalenedecahydride, C,,H,,. 


abt. 190 abt. 0-805(20) | Undekanaphthene, C,,H,,. (Fr. petroleum.) 
194-5ce. -7417°/, Undecane, C,,H,,.—M. p. —26-5°. 


197 -801(20) Dodekanaphthene, C,,H,,. (Fr. petroleum.) 
208-10 -813(20) Tridekanaphthene, C,,H,,. (Fr. petroleum.) 
214-5c. tok /, Dodecane, C,,H,,.—M. p. —12°. 


0 
0 
0 
0 
234 Oeigt %, Tridecane, C,,;H,,..—M. p. —6-2°. 
240—46 0-819(17) Tetradekanaphthene, C,,H,,. (Fr. petroleum.) 
246-8 0-829(17) Pentadekanaphthene, C,,H». (Fr. petroleum.) 
252: 5c. On 6579); Tetradecane, C,,H, —M. p. +5-5°. 
268c. 0-792(14) 7, 8-Dimethyltetradecane, C,,H,,.—Still liq. at —30°. 
270° 5c. 0-7697°/, Pentadecane, C,;H;,.—M. p. 10° 
287 - 5c. Oc4ip/, Hexadecane, C,,H;,.—M. p. 18°. 
303 Genii? /, Heptadecane, C,;H;,.—Does not give Test 901-3. 
Slice. Meili, Octadecane, CisHss.—M. p. 28°.—Does not give Test 901-3. 


Ecc reac aac ara ee -asaicareniniir iiniiraiiniN rage nisin: 


COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I]. 
GENUS IX, HYDROCARBONS. 


DIVISION B, SECTION 2,—LIQUID HYDROCARBONS AND LIQUID 
ALIPHATIC ETHERS WITH SPECIFIC GRAVITY LESS THAN 
0-85 AT 20°/4° THAT ARE ATTACKED OR DISSOLVED EITHER 
IN TEST 901, 902, OR 903. 





Boiling-point 
(G22): 


—102-7 


—85 


—50-2 


abt. —35 


14-5 


18-19 
21-2 


Specific 
Gravity. 


0-610 


0-451(0) 


0-635(13-5) 


0-691(20) 
0-65( —20) 


0-6607°/, 


0-685(0) 


0-670(0) 
0-691°/, 


0-685°/, 


0-69420/, 


HYDROCARBONS, ETC. — Colorless Liquids with Specific 
Gravity less than 0-85 at 20°/4° that are attacked or dis- 
solved either in Test 901, 902, or 903. 





Ethylene, CH,:CH,.—} Easily absorbed by liq. Br, giving 
C,H,Br,, b. p. 180°, m. p. +9-5°. 

Acetylene, CH: CH.—V.d.s. aq.—t} Apply Test 906 w. ammon. 
CuCl sol.! (Dull-red ppt.)—Absorbed in Br gives liq. tetra- 
bromide, b. p. 124°-6° (15 mm.), 

Propylene, Me.CH:CH,.—} The gas is freely absorbed by ec. conc. 
H,SO, or liq. Br.—Dist. of the H,SO, sol. largely diluted w. 
aq. gives isopropyl alc. (cf. Test 818).—B. p. of dibromide 
141-5° ¢.! 

Cyclopropane,(CH,),.—Absorbed slowly by conc. H,SO, or Br. 
—B. p. of dibromide 165°; G, 1-92317°°/,. 

Butadiéne(1, 3), CH,:CH.CH:CH.. 

cis- Butene(2), MeCH:MeCH.—B. p. of dibromide 158°.—Not 
absorbed by conc. H,SO,+4 vol. aq. 

trans-Butene(2), Me.CH: HC.Me.—M. p. of dibromide 161°. 

Methylcyclopropane, Me.C,H,. 

Caoutchene, C,H,.—M. p. —10°. 

Ethylacetylene, Et.C : CH.—Gives Test 906 w. ammon. CuCl.— 
Bromide, C,H,Br,, cryst. solid. 

Butadiéne(1, 2), CH,:C: CH.Me.—Odor like garlic. 

Isopropylethylene, Me,CH.CH:CH,.—I. at 0° in 2 vols. conc. 
H,SO, and 1 vol. aq. 

1, 1-Dimethylcyclopropane, Me,C.(CH,),.—Easily attacked by 
Br, but ‘‘rather stable toward 1% KMnO,.’’—Soluble at 0° 
in 2 vols. conc. H,SO, and 1 vol. aq. 


Butine(2), MeC :CMe.—Strong odor.—B. p. of dibromide 147°-8°. 
—Shaking w. conc. HCl polymerizes to hexamethylbenzene. 


Isopropylacetylene, Me,.CH.C: CH.—Gives Test 906 w. ammon., 
CuCl. 


uns.-Methylethylethylene, MeCEt:CH.,. 


Isoprene, CH,: CH.CMe:CH,.—Very unstable.—Treated w. cone. 
HCl and distilled w. steam leaves rubber-like mass! 


s-Methylethylethylene, MeCH:CHEt.—HI gives methylpropyl- 
carbinol, b. p. 145° 


Trimethylethylene, Me,C: CHMe.—Polymerized by conc. H,SO, 
—S. in 2 vol, H,SO,+1 vol. aq. 


3, 3-Dimethylbutine(1), Me,C.C: CH. 
Propylethylene, PrCH: CH,. 
2-Methylbutadiéne(2, 3), Me,.C:C:CH.,. 





184 


Boiling-point 
(Ec): 


42 
42-5 
45 
48-9 
50 
55-5-6 
59-5c. 


60 
65-7 


68 


68-70 
69-71 


abt. 70 
70 


69-5-71 
70-1 
70°3 
71-2 

71-2-5 
70-74 


72 
72-4 
72-4 

73 


75-80 
77-8 


78-80 
78-80 


78-83 
82-5 


83-4 
83-4 


85-6 


Specific 


Gravity. 


ee) (=) G2) lea) =) 


-80519/, 


-690(20-7) 


-687(19). 


-670(0) 


-785(20) 


-858(18-2) 


-698(19) 
-731(0) 
-763(0) 
-750?"/, 
-732(0) 


-77629/, 
-714(12) 
-712(0) 
-719(21) 
-730(0) 


-751 


-825(0) 


-714(0) 
-738(13) 


GENUS IX, DIV. B, SECT, 2. 


185 


(ORDER I, SUBORDER 1.) 





HYDROCARBONS, ETC. — Colorless Liquids with Specific 
Gravity less than 0-85 at 20°/4° that are attacked or dis- 
solved either in ‘lest 901, 902, or 903. 


Piperylene, CH,:CH.CH,.CH: CH,.—The tetrabromide cryst. fr. 


alc. in pearly ndl., m. p. 114-5°. 

Cyclopentadiéne(1, 3), C;H,.—Conc. H,SO, or HNO, attacks 
violently.—Reduces ammon, AgNO, sol.—Polymerizes easily 
to dicyclopentadiéne, m. p. 32-9°. 

Cyclopentene, C,H,. 

Propylacetylene, PrC :CH.—Gives Test 906 w. ammon. CuCl 
and AgNO. 

Valylene, C,H,.—Odor of garlic_—Test 906 gives yellow ppt.— 
Br gives cryst. hexabromide. 


Valerylene, C;H,.—Test 906 gives no ppt.—Heated w. dil. 
H,SO, gives methyl propyl ketone. 


Diallyl, (CH,:CH.CH,),.—Odor pungent.—H,SO, attacks w. 
violence.—Br gives cryst. tetrabromide, m. p. 63°. 


Pirylene, C,H,.—Peculiar odor.—Test 906 gives no ppt. 

Sty as RES A Me,C: CHEt.—Gives iodide w. HI, b. p. 

42°, 

s-Methylpropylethylene, Pr.CH: CH.Me.—S. in 3 vol. c. H,SO,+ 
1 vol. aq.; the sol. is ppt’d by aq. 

Butylethylene, Bu.CH:CH,. 

1-Methylcyclopentene(2), Me.C,H,.—Oxid. by KMnO, gives a- 
methylglutaric ac. 

Butylacetylene, BuC : CH.—Gives Test 906. 

Diallylene, C,H,.CH,.C: CH(?).—Test 906 gives yellow-green 
ppt.—Alc. AgNO, gives ppt. of Ag compound. 

Methylethylpropylene, Me(Et)C:CH.Me. 

3-Methylpentadiéne(1, 2), Et.C.Me:C:CH,. 

Methyl Butyl Eth., Me.O. Bu.—See Test 907! 

Methylcyclopentane, C,H,,.—Cf. IX, B, 1. 

2-Methylpentine(3), Me,.CH.C: C.Me.—Adds HBr. 

Methyl Isocrotyl Eth., Me,.C: CH.O.Me.—Dec by 2-3 hrs. heat- 
ing at 140° w. 1% H,SO, giving methyl] alcohol and isobutyl 
aldehyde. 

1-Methylcyclopentene(1), Me.C;H,. 

Hexadiéne(1, 3), Et.CH:CH.CH:CH,,. 

$-Ethyldivinyl, CH,: CEt.CH.CH,. 

Tetramethylethylene, Me,.C:C.Me,.—S in 2 vols. conc. H,SO,+ 
1 vol. aq.—Acetone is among products of oxidation by ec. dil. 
CrO, sol. (cf. Tests 702 and 711). 

2, 3-Dimethylpentene(2), Me,.C: C( Me) Et. 

2-Methylpentadiéne(2, 3), Me,.C:C: CH.Me.—W. Br in C8, gives 
C,H,Br, 

Ethyl Isobutyl Eth., Et.0.C,H,.—See Test 907! 

2, 2, 3-Trimethylbutene(3), Me,.C.CMe:CH,.—Odor of camphor 
and turpentine 

Hexadiine(1, 4), Me.C:C.CH,.C:CH.— Polymerizes readily — 
Gives Test 906. 

1, 2-Dihydrobenzene, C,H,. 

2, 5-Dimethylpentene(2), Me,.C:CH.CH.Me,.—Adds HI easily. 

Methylpropylacetylene, MeC? CPr.—CrO, mixture oxid to acetic 
and butyric ac. (cf. Test 702)-—Br reacts violently.—Pro- 
longed shaking w- 5 pt conc H,SO,+1 pt. aq. gives methyl 
butyl ketone. 


1, 4-Dihydrobenzene, C,H,. 


186 


GENUS IX, DIV. B, SECT, 2. 


(ORDER I, SUBORDER I.) 





Boiling-point 
(Ci2)2 


86-7 


92 
92-4 


96-8 
97-8 
98 


98-9 


102 


102-5c. 


103-4 


105 
105-6 
105-8 
108-5 


111-3 
111-4 


112 
113-4 
114-5 

115 
115-5 
116-8 
116-8 
117-1 

116-20 
117-9 
118-9 


120.5-21 


120 
120-1 
19929-5 
122-3 


123-5 
124-6 
131-2 





O- 


O- 


0: 


Specific 
Gravity. 


819(0) 


-752(20) 


-7489/, 
72515 /, 


-703(19-5) 


-751(0) 


715(25) 


803(20) 


-814°/, 
-760(0) 


-796(15) 


-763(0) 


-764(18) 


-841(0) 


-741(22) 
-777(0) 


-759(29/,) 


-769?/, 


-756(21) 
-762(15) 
-760(14) 


-799(0) 
-722(17) 
-770(0) 





HYDROCARS3B0NS, ETC. — Colorless Liquids with Specific 


Gravity less than 0-85 at 20°/4° that are attacked or dis- 
solved either in Test 901, 902, or 903. 


ee eee 


Hexadiine(1, 5), CH:C.CH,.CH,.C: CH.—Ammon. CuCl in Test 
906 gives greenish-yellow ppt.—Alc. AgNO, gives white ppt. 
—Adds Br, violently. 

Ethyl Butyl Eth., Et.O. Buu—See Test 907! 

Ethyl Isocrotyl Eth., Me,.C: CH.O.Et.— Unsat.—Dec. by heating 
w. 1% H,SO, giving isobutyric ald. and C,H,OH. 

3-Ethylpentadiéne(1, 2), Et,.C:C:CH,. 

3-Ethylpentene(2), Et,C: CHMe. 

Heptene(2), Me.(CH,),.CH: CHMe.—CrO, mixture oxid. to va- 
lerianic and acetic acids. (Cf. Test'702.)—In the cold adds 
fuming HCl. 

Heptene(1), Me.(CH,),.CH:CH,.—Does not unite w. cold fum- 
ing HCl. 

CEnanthylidene, Me.(CH,),.C:CH.—Ammon. CuCl (Test 906) 
gives yellow ppt.; ammon. AgNO, also gives ppt.—Gives a 
liq. dibromide. 


Diisobutylene, Me,.C:CH.CMe,.—CrO, mixture, cold, oxid. to 
acetone, etc. (cf. Test 702).—Adds HCl or HI at 100°. 


Heptine, C,;H,,.—Odor peculiar.—Absorbs O.—HNO, attacks 
violently.—H,SO, polymerizes to diheptine, b. p. 247°.— 
Adds Br.—Does not give Test 906.—(FY. dist. of rosin.) 

Toluenetetrahydride, Me.C,H,.—Nitrated by nitrosulphuric ac. 

Ethylpropylacetylene, PrC: CEt.—H,SO, gives butyrone. 

Dihydrotoluene, Me.C,H,. 

I, I, 2-Trimethylcyclopentene, C,H,,.—Faint odor like camphor 
and turpentine. 

Methylbutylacetylene, Me.C:C.C,H,.—Alc. AgNO, gives no ppt. 


Ethyl Valeryl Eth., Me.C(Et):CH.O.Et.—Heated w. 1% H,SO, 
at 130°-40° gives methylethylacetaldehyde and C,H,OH. 


Ethyl Isoamyl Eth., Et.0.C,H,,.—See Test 907! 

2, 5-Dimethylhexadiéne(1, 5), CH,:C(Me).CH,.CH,.C(Me) :CH.. 
Cycloheptene, C,H... 

Heptone, C,H, ,.—Gives oily hexabromide, C,H,,Br,. 
s-Dimethyldiethylethylene, Me,C: CEt,. 


-Hexeny]l Eth., (C,H,,),.0.—Oil w. very pungent odor; i. aq. 


2-Methylheptadiéne (4, 6), C,H,,. 

Propyl Butyl Eth., Pr.O. Buu—See Test 907! 

s-Diisopropylethylene, Pr.CH:CH.Pr. 

Octadiéne(2, 6), C,H,,. 

Hexahydro-m-xylene, Me,.C,H,,.—Hot nitrosulphuric ac. gives 
trinitro-m-xylene, m. p 172°-4° 

Hexahydro-p-xylene, C,H,,(CH;),.—E. s. on warming in mix. of 
HNO, and H,SOQ,. 

Allyl Isoamyl Eth., C,H,.0.C,H,,. 

sec.- Butyl Eth., (Me(Et).CH).0. 

Isobutyl Eth., Bu,.0.—See Test 907! 

4-Ethylhexadiéne(1, 4), CH,:CH.CH,.CEt: CHMe.—Absorbs O 
fr. air slowly.—CrO, mixture oxid. to Ac and propionic ac. 
(Tests 905-2 and 311) 

Glycol Diethyl Eth., C,H,.(OEt),.—See Test 907! 

Octene(1), C,H,;.CH: CH,. 

Octine(1), C,H,,.C :CH. 


GENUS IX, DIV. B, SECT, 2. 187 


(ORDER I, SUBORDER I.) 


es 3 “40s HYDROCARBONS, ETC. — Colorless Liquids with Specific 
case cere Gravity less than 0-85 at 2U°/4° that are attacked or dis- 
solved either in Test 901, 902, or 903. 





132-4 0-773(18) 2, 5-Dimethylhexadiéne(2, 4), Me,C: CH.CH: CMe,.—M. p. + 6°. 
—Very unstable, absorbing O rapidly fr. the air—Polymer- 
izes on keeping.—Gives liquid tetrabromide. 


132-4 0-828(20) m-Dihydroxylene, Me,.C,H,.—Conc. HNO, gives nitro-m-xylene- 
133-4 Octine(2), Me.(CH,),.C: C.Me.—The tetrabromide is oily. 
133-5 Octone, C,H,,.—Absorbs O fr. air.—Br or HCl gives a resin. 
134-5 o-Dihydroxylene, Me,.C,H,.—Odor like camphor.—Quickly 
oxid. in air to a resin.—Adds HCl in eth. sol. 
134-5-5-5 p-Dihydroxylene, Me,.C,H,.—Odor like turpentine.—HBr gives 
cryst. addition product. 
134-7 Ethyl Hexyl Eth., Et.0.C,H,,—See Test 907! 
abt. 135 0-803(20) Campholene, C,H,,.—Odor like turpentine.—Absorbs Br, in dil 
CHCl, sol. 
138 0-798(22) Trimethylcyclohexene, C,H,,. 
139-5ce. 0-7437°/, Merona C,H,,.—(Several isomers boiling between 140° and 
Om 
141 0-769(20) Butyl Eth., Bu,O.—See Test 907! 
140-1 0-8357°/,, Pe atts SA Diethyl Eth., (CH,);.(OEt),.—Fruity odor. 
—I. aq. 
141-5 2-Methyloctene(1), Me.C(C,H,,) : CH,.— Odor aromatic. 
142-3 0-757(20) 2, 6-Dimethylheptadiéne(2, 6), C,H,,. 
145 0-831(15) Octylene Oxide, C,,H,,0. 
145-50 Decone, C,,H,,.—Odor like turpentine.—Absorbs O rapidly. 
147-5-9-5 Propylhexamethylene, Pr.C,H,,. 
149-8 0-795(0) Methyl Heptyl Eth., Me.0.C,H, See Test 907! 
150 Decenylene and Rutylene, C,,H,,. 
150-2 1, 2-Methylethylcyclohexane, Me.C,H,,.Et. 
153 1, 2-Dimethylcycloheptane, Me,.C,H,.. 
154-6 0-772(20) Diamylene, C,)H.». 
155-7 Nonone (Carpene), C,H,,.—Oxid. to a resin in the air. 
156 -86(20) Pinene (Terebenthene), C,,H,,.—Cf. (IX, B, 3). 


0 
158 0-7667!/, 4-Propyl-3, 6-heptadiéne, C,,H,,.— Unstable oily tetrabromide. 
166 0-795(0) Ethyl Heptyl Eth., Et.0.C,H,,.—Cf. Test 907! 
0 


167 - 4c. -806°/, Menthene, C,,H.,.—Opt. act —Easily oxid. by shaking with c 
1% permanganate sol.—(Descriptions conflicting.) 


167-70 3, 6-Dimethyloctadiéne(3, 5), C,)H,s. 


171-2 0-856(10) Phellandrene, C,,H,,.—Cf. (IX, B. 3). 
173 0-801(0) Methyl Octyl Eth., Me.0.C,H,,—Cf Test 907! 
173c. 0 781(15) t Isoamyl Eth., (C;H,,),.0.—Cf Test 907! 
175 (th. 1.) 0 853(25) Cymene, C,,H,,. 
176-7 0-851(16) Sylvestrene, C,,H,,.—(In Swedish turpentine oil.) 
176-5 0-853""/, [+ or —] Limonene, (Hesperidene, Citrene, Carvene), C,,H,..— 
([+] variety in lemon oil, etc )—Cf IX, B, 3. 
173-80 0-8371°/, Naphthalenedecahydride, C,,H,,.—Hot fuming HNO, attacks 
violently. 
177-8 0-774(0) Triisobutylene, Me,.C:C.(CMe,),.—Oxid. slowly in air; Br acts 
w. violence. 
180 Diallyl Eth., (C,H,,),.0. 
179-82 Terpinene, C,,H,,.—Cf. IX, B, 3. 
181-2 0-844(20) i-Limonene, C,,H,,.—Odor like oil of lemons —Cf. IX, B, 3. 


183-5c. Terpinolene, C,,H,,.—Cf. IX, B, 3. 





188 GENUS IX, DIV 75, 8hCig: 


(ORDER I, SUBORDER I.) 





ap ; ; HYDROCARBONS, ETC. — Colorless Liquids with Specific 
ea ean recipe Gravity less than 0-85 at 20°/4° that are attacked or dis- 
solved either in Test 901, 902, or 903. 


189.2 0-801(0) Ethyl Octyl Eth., Et.0.C,H,,—Cf. Test 907! 


abt. 195 abt. 0:8 Undecylene, C,,H,,. 
196-8c. 0-8397°/, Dodecon, C,,H».—Easily oxid.—Action of Br violent. 
abt. 210-15 Undecine, C,,H...—Ammon. AgNO, gives white ppt. 
213-215 0-785(20) Duodecylene, C,,H,,.—(Fr. Canadian petroleum.) 
2338¢. 0-845(0) Tridecylene, C,,H,,.—(Fr. Burmese petroleum.) 
245-8 0-814 Triamylene, C,,H.—Turpentine odor.—Adds Br, cold. 
261 0-815(0) Heptyl Eth., (C,H,,;),.0.—Cf. Test 907! 
274 0-7841°/, Cetene, C,,H;..—Br gives dibromide.—M. p. 4°. 
280-5 0-8047°/, Cetylene, C,,H5.—M. p. 20°. 
291-7 0-820(0) Octyl Eth., (C,H,7),.0.—Cf. Test 907! 
314-5 0-818(24) Eicosylene, CH;,. 








COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER J]. 


GENUS IX, HYDROCARBONS, ETC. 


DIVISION B, SECTION 3,—LIQUID HYDROCARBONS AND ETHERS 
WITH SPECIFIC GRAVITY GREATER THAN 0.85 AT 20°/4°. 


Boiling-point 
(Ce). 
31-5 


67 
80-36 
93 


111 
114 


120-1 
136-5 (th. i.) 
138 


139-2 
141-6 (th. i.) 


142c. 
143-5 
146 


152-5-3 
155 


155 


156 


Specific 
Gravity. 


0-944(15) 


0-950(15) 
0-879/, 
0-90377/, 


0-866?°/, 
0 913°/, 


0-893°/, 
0-883(0) 
0-880(0) 


0-86629/, 
0 -9307°/, 


0-893(0) 
0-890(0) 
0-925(0) 


0-859(25) 


0-98871/, 


0-86(20) 


0-870%8/, 
0-873(16) 








HYDROCARBONS, ETC. — Colorless Liquids with Specific 
Gravity greater than 0-85 at 20°/4°. 


Furfurane, C,H,O.—Peculiar odor.—I. aq.; e. s. ale. or eth.— 


Colors a pine splinter moistened w. conc. HCl emerald green! 
—Conc. HCl attacks vigorously giving a brown resinous body. 

Hydrofurfurane, C,H,O (?).—Adds Br, cold.—Not attacked by 
Na, KOH, or acetic anhyd.—PCl, gives furfurane. 

+ Benzene, C,H,.—M. p. 5-42°.—Identify by Test 913! 

2, 5(a)-Dimethylfurfurane, Me,.C,H,O.—I. aq.; misc. w. ale.— 
Conc. HCl changes to a resinous body.—Dil. HCl at 170° 
gives acetonylacetone. 

+ Toluene, Me.C,H,.—Identify by Test 918! 

Tropilidene, C,H,.—CrO, mixture (cf. Test 905-2) gives benzoic 
ac. (cf. Test 312) and benzaldehyde.—Br gives an oily di- 
bromide. 

Cycloheptadiéne, C,;H,,.—Odor garlicky. 

{ Ethylbenzene, Et.C,H,.—} Oxidize 1 grm. to benzoic ac. by 
Test 905-1! 

+ p-Xylene, Me,.C,H,.—M. p. 15°.—Identify by Test 920! 


; + m-Xylene, Me,.C,H,.—M. p. —54°.—Identify by Test 919! 


Phenylacetylene, PhC: CH.—Test 906 w. ammon. CuCl gives a 
yellow flocculent ppt. fr. alc. sol., which when dry detonates 
on heating.—HNO, or conc. H,SO, resinifies.—7} Heated w. 
dil. H,SO, gives acetophenone (Test 712). 

+ o-Xylene, Me,.C,H,.—M. p. —28°.—Identify by Test 921! 

Crotonyl Eth., (Me.CH:CH.CH,),.0. 

Styrene, PhCH:CH,.—I. aq.; misc. with alc. or eth.—Slowly 
polymerizes to glassy mass;—conc. H,SO, polymerizes im- 
mediately.—Gives Test 903!—Odor aromatic and rather 
characteristic. 

Cumene, Ph.CH.Me,.—Test 905-1 gives benzoic ac. (Test 312). 

Benzylethylene, Ph.CH,.CH:CH,.—Unsat. (cf. Test 901).—Test 
905-1 gives benzoic ac. (Test 312). 

Anisol, Me.0.Ph.—Aromatic odor !—I. aq.—W. conc. HI] at 130°- 
40° gives phenol and methyl iodide. 

Pinene (Terebenthene), C,,H,,.—(The chief constituent of { oil 
of turpentine). The American or English, fr. Pinus Aus- 
tralis, is[+]; the French, fr. Pinus maritima, is [—].—Odor 
penetrating and characteristic.—Gives Test 901.—Fum- 
ing HNO, attacks w. almost explosive violence.—Well 
cooled and saturated w. dry HCl gas, gives hydrochloride 
(C,)H,,-HCl), stable volatile cryst. (m. p. 125°), fr. dil. alc., 
and of camphor-like odor (“‘ artificial camphor”’),. 

Propylbenzene, Pr.C,H,.—Test 905 gives benzoic ac. 

o-Methylethylbenzene, Me.C,H,.Et.—Oxid. by Test 905-3 gives 
phthalic ac. 


a“. 


189 


190 


Boiling-point 
(C.°). 


158-9 


160-2 
162 


164 
164-5 
167-8 

168-8 -5 


169-8c. 


170-72 
171-1-5 
171-3 
171-2 
170-5 
172 


173 


174-5 


170-80 
175 (th. i.) 


175 
175-5 -5 
175-6 


176c. 


176 


176-5 


Specific 
Gravity. 


0-869(20) 


0-788?°/, 
0-865(21) 


0-7939/, 
0-869°8/, 
-938(18) 


co) 


iS 


-87929/, 


-873(16) 
-858(15) 
-996(0) 

-856(10) 


2) je) == 


0-982(0) 


0-846(23) 


0-918'5/,, 


0-853(25) 


0-987(0) 


0 -862(20) 


0-957(15) 


© 


-927(20) 


0+85319/, 


GENUS IX, DIV. B, SECT. 3. 


(ORDER I, SUBORDER I.) 


HYDROCARBONS, ETC.—Colorless Liquids with Specific Grav- 
ity greater than 0-85 at 20°/4°. 





m-Methylethylbenzene, Me.C,H,.Et.—Test 905-1 gives iso- 
phthalic ac. 

a-Terpenetetrahydride, C,,H,,.—(Cf. IX, B, 1.) 

p-Methylethylbenzene, Me.C,H,.Et.—Test 905-1 gives tere- 
phthalic ac. (Test 318-3). 

6-Terpenetetrahydride, C,,H,,.—(Cf. IX, B, 1.) 

t Mesitylene, C,H,.Me,(1:3:5).—Identify by Test 914! 

Methyl Benzyl Eth., C,H,.0.Me. 

tert.-Butylbenzene, Ph.C.Me,.—Oxidation (cf. Test 905) gives 
benzoic ac. 


t+ Pseudocumene, C,H;.Me,(1, 2, 4).—For coloration w. AICI, cf. 
Test 904.—Identify by Test 917! 


sec.- Butylbenzene, Me.CHEt.C,H,.—Test 905 gives benzoic ac, — 
Isobutylbenzene, Ph.CH,.CHMe,.—Test 905 gives benzoic ac. 


o-Cresyl Methyl Eth., Me.O.C,H,. 

[+] Phellandrene, C,,H,,.—(In fennel and other essential oils.) — 
I. ale.; s. eth.—Identify as nitrosite. (Cf. A, 246, 282; and 
287, 374.) 


p-Methylstyrene, Me.C,H,.CH:CH,.—Unsat. (cf. Test 901).— 
Test 905-1 gives terephthalic ac. (Test 318). 


Phenetol, Et.O.Ph.—Odor aromatic.—I. aq.—At 400° gives 
phenol (Test 414) and ethylene. 


Amenylbenzene, Ph.CH(Et).CH:CH,.—Gives Test 901.—Con- 
tinued boiling gives diamenylbenzene, b. p. 208°-12°.—Test 
905 gives benzoic ac. (Test 312). 


Allylbenzene, PhCH: CHMe.— Unsat. (cf. 901).—Dibromide, ndl. 
d.‘s..c.-alc.,;m..p2 00a 


Diamylene Oxide, C,,H,,0.—Reduces ammon. AgNO, sol. 


Cymene, p-Me.C,H,.CHMe,.—Test 905-2 gives terephthalic ac. 
(Test 318). 


p-Cresyl Methyl Eth., Me.0.C,H,. 
I, 2, 3-lrimethylbenzene, C,H,.Me,. 


m-Methylisopropylbenzene, Me.C,H,.Pr.—Br substitutes readily 
cold.—Test 905-2 gives isophthalic ac. (Test 318). 


1, 2-Hydrindene, C,H,:C,H,:CH,.—Br substitutes. — Sulpho- 
nated by cold conc. H,SO,. M. p. sulphonamide 91°-2°, 


} Eucalyptol (Cineol), C,,H,,0.— Agreeable odor like car- 
damon and camphor!— M. p. —1°-3°.— Unsat.; dibro- 
mide very unstable-—Dry HCl conducted into mixture 
of equal vols. eucalyptol and lgr. gives cryst. ppt. of 
unstable (C,,H,,O),.HCl.—Shaken w. saturated sol. of I 
in saturated KI sol. gives ppt. of minute cryst. w. greenish 
lustre. 


[+ or —]Limonene (Hesperidene, Citrene, Carvene), C,,H,,. 
—({+] in oil of lemons.) —General behavior in Test 
901-3 as with pinene.—Dilute w. 4 vol. glac. Ac, cool 
well, and drop in Br as long as color disappears. Allow 
to stand until crystals separate. Drain, and then recryst 
fr. acetic ether. The tetrabromide formed melts at 104-5°. 
(A, 239, 3)! 





Boiling-point 
TCLS). 


— 


176-7 


176-8 
176-8 


178 
180 
180c. 


179-82 


180-1 


181 (th. i.) 


181-2 


181-2 


182-3 
183-4 


183-4 


183-5c. 


185 
185 


185 


185 
186-7 


186-8 
185-90 
185-90 


189 


189-5-91 


0-851(16) 


om) 


O- 


O- 


Specific 
Gravity. 





-901(15-5) 


-873(21) 


-864(15) 
-040(15) 


958 


844(20) 


-860°/, 


-86218/, 
-878(20) 


-942(0) 


-86618/, 


-861(20) 


-892?2/, 


-966(0) 
-874(15) 


GENUS TX, DIV. B, SECT. 8, 191 


(ORDER I, SUBORDER I.) 


HYDROCARBONS, ETC. — Colorless Liquids with Specific 
Gravity greater than 0-85 at 2u°/4°. 





[+] Sylvestrene, C,,H,,.—(In Russian and Swedish turpentine 
oils.) —The sol. in acetic anhyd. is colored intensely blue by 





| a drop of conc. H,SO, (a reac. that may be interfered with 


by the presence of some other terpenes).—Br in Ac sol. (pro- 
cedure as w. limonene above) gives tetrabromide, m. p. 
135°-6°; but it is said to be preferable to identify as dihy- 
drochloride, m. p. 72° (cf. A, 230, 241; 239, 25), obtained by 
action of dry HCl gas. 

p-Butyltoluene, Bu.C,H,.Me.—Oxid. by dil. HNO, (Test 905-3), 
giving p-toluic ac. 

Phenylbutylene, Ph.C,H,,—Unsat. (cf. Test 901).—Test 905-1 
gives benzoic ac. 

Diethylphenylmethane, Ph.CH.Et,.—Test 905-1 gives benzoic ac. 

Butylbenzene, C,H,.C,H;.—Test 905-1 gives benzoic ac. 

1, 2-Indene, C,H,.—(In light coal-tar oils.)—Conc. H,SO, gives 
brown resin.—Adds Br.—Forms picrate.—Dil. HNO, gives 
phthalic ac. 

Terpinene, C,,H,,.—(In cardamon and other essential oils.)— 
Opt. inactive.—Resinifies on keeping, or by action of conc. 
H,SO,.— Unlike pinene is completely destroyed in the cold 
(except a few brown flocks) by a mixture of 6 pt. Na,Cr,O,, 
5 pt. H,SO,+30 pt. aq.—For identification as nitrosite, see 
A, 239, 36! 

o-Cresyl Ethyl Eth., Et.0.C,H,. 

Isobutenylbenzene, Ph.CH: CMe,.—Test 905-2 gives benzoic and 
acetic acids.—Br gives liq. bromide. 

i-Limonene, C, ,H,,.—(Syn.-Dipentene, diisoprene, cinene, caout- 
chin, etc.)—Odor lemon-like.—Absorbs O fr. the air.—Pre- 
pare the tetrabromide, m. p. 124°-5°, by the procedure given 
under + or — limonene on p. 190! 

m-Diethylbenzene, C,H,.Et,.—Oxid. by Test 905-1 gives iso- 
phthalic ac. (Test 318). 

p-Diethylbenzene, C,H,.Et,.—Test 905-1 gives terephthalic ac. 

I, 3, 4-Dimethylethylbenzene, Me,.C,H,.Et.—May be oxidized 
to xylic ac. 

Pinol, C,,H,,0.—Odor like that of eucalyptol !—Unsat.—Dis- 
solved in 2 vols. glacial Ac and treated w. Br, gives stable 
dibromide which cryst. well fr. eth.-alc. w. m. p. 94°. 

Terpinolene, C,,H,,,. 

o-Diethylbenzene, Et,.C,H,.—Test 905-1 gives some phthalic ac. 

Ethyl Benzyl Eth., Et.0.C;,H,.—Treatment w. P,O, gives ethyl- 
ene and anthracene (Test 912). 

I, 3, 5-Dimethylethylbenzene, Me,.C,H;.Et.—Test 905-2 gives 
mesitylenic ac. 

Phenylallylene, Ph.C:C.Me.—Tetrabromide, lft. fr. alc., m. p.75°. 

1’-Butenylbenzene, Ph.CH: CHEt.— Unsat. (cf. Test 901).—Test 
905-1 gives benzoic ac. (Test 312). 

m-Pseudobutyltoluene, Me,C.C,H,.Me.—Test 905-2 gives iso- 
phthalic ac. (Test 318). 

Phenylcrotonylene, Ph.C,H,.—Unsat. (cf. Test 901).—Test 905-1 
gives benzoic ac. (Test 312). 

Naphthaleneoctahydride, C,,H,,—Odor like turpentine.—Ab- 
sorbs O fr. air. 

p-Cresyl Ethyl Eth., C,H,.0.Et. 

Dimethylethylphenylmethane, Me,(Et)(Ph).C.—Br substitution 
product is oily. 





192 


Boiling-point 
(Coy: 


190-2 
193 
194-5 
195 
195-7 


198-200 
199-200 


201 
201-3 


200-5 
204 (th. i.) 


205 (th. i.) 


abt. 205 (th. i.) 


205-6 


205-6 


206-7 
206-10 


208-8 -5 
209 
211-13c. 


212 


213 


214-15 
214-15 
216-2 

214-18 


215-20 
220-5-1-5 


223-8 
226-9 


229-30 


O- 


0 


O- 


1 


O- 


O-: 


O- 


0. 


0 


GENUS IX, DIV. B, SECT. 3. 


(ORDER I, SUBORDER I.) 





Specific HYDROCARBONS, ETC. — Colorless Liquids with Specific 
Gravity. Gravity greater than 0-85 at 20°/4°. 





1, 3-Ethylisopropylbenzene, Et.C,H,.Pr.—Test 905-1 gives iso- 
phthalic ac. (Test 318-2). 


-885(18) Isoamylbenzene, Ph.C,H,,.—Slowly oxid. by Test 905-2 to ben- 


zoic ac. (Test 312) eure in sunlight gives Br derivative, m 
p. 128°-9°. 

Isopropyl-m-xylene, Pr.C,H,.Me.. 

m-Tolylbutylene, C,H,.C,H,—Unsat. (cf. Test 901); the di- 
bromide is oily. 

-896°/, I, 2, 3, 5-Letramethylbenzene, Me,.C,H,.—Test 905-1 gives only 

mellophanic ac., m. p. 238° d. 

p-Tolylpropylene, C,H,.C,H,.—Unsat. (cf. Test 901). 


-879(20) (s), I, 3, 5-Diethyltoluene, Et,.C,H,.Me.—Test 905-3 gives uvitic 


ac., m. p. 287°-8°. 


-860(22) Amylbenzene, C,;H,,.C,H;.—Test 905-2 gives benzoic ac. (Test 


312). 


-923(21) Ethylphenylacetylene, PhC : CEt.—Unsat. (cf. Test 901). Test 


905-1 gives benzoic ac. (Test 312). 

Ethylbutylbenzene, C,,H,,. 

1,2; 3) 4-Tetramethylbenzene, Me,.C,H, sae cryst., p. 
’"4°.—Test 905-3 gives prehnitic ac. (TIT, Ai mas 2375), 

981(12-5) | Naphthalenetetrahydride, C,,H,,— Feeble odor. Tea 905 gives 
phthalic ac.—Conc. HNO, gives picric ac.—Oxid. on stand- 
ing in air.—Br gives unstable substitution product. 

-93473/, Naphthalenehexahydride, C,,H,,.—Absorbs O fr. air.—HNO, or 
cold Br attacks w. violence .—Fuming H,SO, sulphonates. 

96877 /, y-Methylindene, C,,H,,.—Naphthalene odor.—Absorbs O fr. air. 
—Conc. H, So, or HCl resinifies—Forms very unstable pic- 
rate, m. p. "75° Gu, 

-086(15) Veratrol, o-C,H,.(OMe),.—Solid at 15°.—Heated w. HI gives 
pyrocatechin and methyl iodide. 

Propyl-p-xylene, Pr.C,H,;.Me,. 

s-Dimethylpropylbenzene, Me,.C,H,.Pr(3:5:1). — Test 905-3 
gives mesitylenic ac. (III, A, 2, m. p. 166°). 

Propyl-m-xylene, Pr.C,H,.Me,(4, 3, 1). 

Propyl-o-xylene, Pr.C,H,.Me,(4, 2, 1). 

871(0) p-Propylisopropylbenzene, Pr.C,H,.Pr.—Test 905-3 gives tere- 
phthalic ac. and Poe ac. 

Naphthalenedihydride, C,,H,,.—Frozen at +15-5°.—Adds Br, 
in the cold; m. p. of unstable dibromide 74° .—Fuming H,SO, 
sulphonates. 

-864(9) p-Isoamyltoluene, Me.C,H,.C,H,,.—Test 905-2 gives terephthalic 

ac. (Test 318-3). 


857(16) Isohexylbenzene, Ph.(CH,),.CHMe,. 
-080°/, Dimethyl Resorcinyl Eth., m-(MeO),.C,H,.—-Vol. w. st. 
953(0) Methyl Thymy] Eth., Me. 0. C, His 
s-Triethylbenzene, C, A, .Et,.—Test 905-2 gives trimesic ac. (IIT, 
A, 1, m. p. 345°-5 50°). 
920747; Issey) Phenyl Eth., C,H,,.0.Ph. 


Ny Ba a Dre C,H,.—Test 905--3 gives p-propylbenzoic 
en( Lil A, 2,miap. 140°). 


-911(0) Beaticass C,H... eee (cf. Test 901). 

-933(0) Ethyl Thymyl Eth., Et.0.C,,H,;.—At 360°—400° splits to thymol 
and ethylene. 

-890(15) Allylisopropylbenzene, Me.CH: CH.C,H, C,H, .—Adds Br, to form 


dibromide, v. s. h. alc., m. p. 59°. 





Boiling-point 
(Ex): 





233 


233c. 
233 


230-40 
240-2 (th. i.) 
242 (th. i.) 


244 
250 (th. i.) 


251 
258 sl. d. 


258-60 
261-2 


261-3 
262-4 
263-7 


265 


250-80 


265 
269c. 


270-5 


272-7 
275 (th. i.) 


abt. 275 
275-5 (th. i.) 


277 (th. i.) 


Specific 
Gravity. 


1-108(15°) 


0-989(28) 


1-001(19) 


1-008(0) 


1-018'°/,, 


1-0017°/, 


0-849(15) 


1-020(12) 


1-015(27) 
0-990(0) 


0-904-0- 927 


0-887(0) 
1-096'4/, 


0-933(20) 


1-031(0) 
0-929(0) 


0-997(17-5) 


0-899(19) 


GENUS IX, DIV, By, SECT.3, 


193 


(ORDER I, SUBORDER I.) 





HYDROCARBONS, ETC. — Colorless Liquids with Specific 
Gravity greater than 0-85 at 20°/4°. 





Safrol, C,H;.(C,;H,;)(O,CH,)[1:(3, 4)]—Strong sassafras odor! 


M. p. after solidification by cold+11°; N,=1-53836.— 
Quickly reduces a 1% neutral KMnOQ, sol. upon shaking. Is 
violently attacked and completely carbonized in Test 907 
with conc. H,SO,. 


Anethol, Me.0.C,H,.—Cf. IX, A, m. p. 21-6°. 


‘Heptylbenzene, C,H,,.C,H,.—(Several compounds isomeric w. 


this substance w. b. p.’s between 225°-48° have been de- 
scribed.) 

Diisobutylbenzene, (C,H,),.C,H,. 

a-Methylnaphthalene, C,,H,,.—Freezes at —22°.—Long boiling 
w. conc. HNO, gives isonaphthoic acid, C,,H,O,.—Picrate fr. 
alc. forms yellow ndl., m. p. 116°. 

(-Methylnaphthalene, C,,H,,.—M. p. 32-5°.—The picrate forms 
yellow ndl. w. m. p. 115°. 

Dimethyl Orcinyl Eth., (MeO),.C,H,.Me.—Alm. i. aq. 

I, 2, 4, 5-letraethylbenzene, Et,.C,H,—M. p. 13°.—Oxid. gives 
pyromellitic ac. (III, A, 1, m. p. 264°). 

-Ethylnaphthalene, Et.C,,H;.—The picrate cryst. fr. h. alc. in 
fine yellow ndl. w. m. p. 69°-71°. 

a-Ethylnaphthalene, Et.C,,H;— Forms a picrate, lemon-yellow 
nd!., m. p. 98°. ; 

Phenyltolyl, Ph.C,H,. 

Diphenylmethane, Ph,.CH,.—Ndl. m. p. 26°-7°.—Cf. Div. A of 
this genus. 

Octylbenzene, C.H,,.C,H;.—M. p. —7°.—Test 905-2 gives ben- 
zoic ac. w. difficulty.—(Isomeric hydrocarbons exist w. b. 
p.’s between 230°-260°.) 

1, 4-(a)Dimethylnaphthalene, Me,.C,,H,. — Remains liq. at 
—18°.—Picrate forms orange ndl., m. p. 139°; s. h. alc.; 
v. s. eth. 

p-Phenyltolyl, Ph.C,H,.Me.—Freezes at —2°-3°. 

$-Propylnaphthalene, C,,H,;.Pr.—Picrate lemon-yellow ndl., m. 
p. 89°. 

Sesquiterpenes, C,,H,,.—(Important constituents of many essen- 
tial oils, like oils of cedar, calamus, cubebs, patchouli, etc.) 
—D. s. ale.; somewhat viscous.—Give solid hydrochlorides 
when HCl gas is passed into the cooled ethereal sol. 

Diisoamylbenzene, (C,H,,),.C,H,.— Liq. at — 20°. 

Methyl a-Naphthyl Eth., Me.0.C,,H;.—Gives red cryst. comp. 
w picric ac.—Split by conc. HCl at 150°. 

Phenanthreneperhydride, C,,H,,.—M. p. —3°.—Not attacked 
cold by fuming HNO,, by H,SO,, or Br, and by CrQ, only w. 
difficulty. 

m-Phenyltolyl, Ph.C,H,.—‘‘ Not attacked by KMnO,.” 

Cadinene, C,;H,,.—(A sesquiterpene present in cubeb, patchouli, 
and some other essential oils.)—D. s. ale-—Resinifies easily. 
—Gives a solid dihydrochloride, m. p. 117°-18°.—When 
slightly resinified and dissolved in much glacial Ac becomes 
green and then indigo-blue on addition of small successive 
portions of conc. H,SQ,. 

o-o and o-p-Ditolyl, (Me.C,H,),. 

m-Benzyltoluene, Ph.CH,.C;H,—Much conc. HNO, at 90° gives 
nitro-compound, cryst. fr. h. glacial Ac, m. p. 141°. 

Pentaethylbenzene, C,H.Et;.—Dec. by fuming H,SQ, to tetra- 
ethvl- and hexaethyl-benzene. 


a jl a a ee SS ee 


194 GENUS IX, DIV. B, SECT. 3. 


(ORDER I, SUBORDER I.) 


-_ 











Boiling-point Specific. HYDROCARBONS, ETC.—Colorless Liquids with Specific 

(C.°). Gravity. Gravity greater than 0-85 at 20°/4°. 

277 a-Diphenylethylene, C,,H,,.—CrO, mixture oxid. to benzophe- 
none. (Unsat.—Br addition product unstable.) 

277-90c. 0-996(0) a?-Diphenylpropane, Me.CHPh.CH,.Ph. 

280 $-Isobutylnaphthalene, C,H,.C,,H;—The picrate forms yellow 
ndl., e. s. alc., m. p. 96°. 

280-1 3-Bitolyl, C;H,.C;H:.—CrO, oxid. to isophthalic ac. (cf. Tests 
905-2 and 318). 

28 1c. 1-075°/, Ethyl a-Naphthyl Eth., Et.0.C,,H,. 

281-2 Dimethyldiphenylmethane, Me,.C.Ph,. 

283-4 1-043 m-Ethylbiphenyl, Et.C,H,.Ph.—CrO, oxid. to m-phenylbenzoic 
ac CLLL AS 23m 1607), 

286 0-98 p-Phenyltolylethane, Ph.C,H,.C;H;.—M. p. 27°. 

286 Ditolylmethane, CH,.(C,H,Me),.—M. p. 22°-3°.—Slowly_sul- 
phonated by fuming H,SO,—CrO, oxid. to dimethylben- 
zophenone. 

288 0-999'°/, o-m-Bitolyl, C;H,;.C;H-.—CrO, oxid. to isophthalic ac. (Test 
318). 

293-4 0-987(15) s-Benzyltolylethane, C,H,.C,H,.C,H,.Me. 
293-5 p-Ethyldibenzyl, Ph.CH,.CH,.C,H,.Et.—_Shows bluish fluores- 
cence. 

294 Benzyl-p-xylene, Ph.CH,.C,H,.Me,. 

294-5 (th. 0-985(18-9) | Ethylbenzylbenzene, Et.C,H,.CH,.Ph.—H. s. alc., eth., or CHCl,. 
295-8 0-9747/, p.-Ditolylethane, Me.CH.(C,H,)..—Test 905-2 gives dimethyl 
phenyl ketone and tolylbenzoic ac. 
295-8 (th. i.) 1-036(16) Benzyl Eth., (Ph.CH,),.0.—Heated above 315° yields benzal- 
dehyde, toluene, and resinous matter. 
304-5 Ditolylethylene, (Me.C,H,),.C : CH,.—Test 905-2 gives ditolyl 
ketone, m. p. 94°.—Dibromide v. unstable, losing HBr. 
308 0-969(15) Benzylcymene, C,H,.C,H;.(Me)Pr. 
310 (th. i.) 1-067(10-2) | Phenanthrenetetrahydride, C,,H,,.—Oxid. by CrO, in Ac sol. to 
anthraquinone (Test 1011). 
a. 300 0-939 Diterpenes, C,,H,,.—(In copaiva balsam, etc.)—Very viscous; 
Lalc: ; 
323-5 0-9667°/, m-Dixylyl-ethane, (C,H;.Me,),.CH.Me.—Exhibits a blue fluo- 
rescence. 

324c. a, §-Phenylxylylpropane, Ph,(C,H,.Me,).C,H,. , 

324-5 a-Phenylnaphthalene, Ph.C,,H,,—Shows a feeble blue fluores- 
cence.—Oxid. to o-benzoylbenzoic ac. in alkaline sol. 

343-6 0-969(18) Diterebenthyl, C,.H.—Absorbs O fr. air.—Is easily oxid. by 
oxid. agents.—Not attacked by cold H,SO,.—_Fuming HNO, 
nitrates.—Br substitutes. 

350 Cuminyl Eth., (C,)H,;)..0.—Dist. w. partial dec. to cymene and 
cuminic aldehyde. 

392-6 1-049 Dibenzyltoluene, Me.C,H;.(CH,Ph),. 

392-6 Dixylylbenzene, C,H,.(CH,.C,H,.Me),.—E. s. alc., eth., or Ac. 
390-400 0-871(0) Tetramylene, CH,). 
396-400 s-Triphenylethane, Ph.CH,.CH.Ph,.—Shows a violet fluorescence. 


—_—_—___- SS 


NUMBERED SPECIFIC AND SEMI-SPECIFIC TESTS FOR 
SPECIES OF GENUS IX. 


[TESTS 901-1000] 


go1. Bromine Test for Unsaturation. 


This test for unsaturation finds many applications, but is most frequently employed 
in connection with the species of Genera IX and III. 

Dissolve or suspend 0.1 grm. of the pure compound—finely powdered, if it is an in- 
soluble solid—in 2 cc. of dry carbon tetrachloride in a three-inch test-tube. Add three 
drops of a bromine solution * prepared by dissolving 2.0 cc. of bromine in 50 cc. of carbon 
tetrachloride. If decolorization does not take place at once, stopper the tube loosely, 
and allow to stand for three minutes in the cold, shaking occasionally if the body is insoluble. 
If the solution becomes colorless before the end of two minutes, drop in more bromine 
solution until a color that is permanent for a minute or two is produced. Then blow 
sharply across the mouth of the tube, and notice whether a white cloud (hydrated hydro- 
bromic acid) makes its appearance. 

If no signs of action in the cold are observed, hold the tube high above a small flame 
and boil very gently for two minutes. If decolorization results, drop in more bromine 
until the coloration remains permanent for nearly a minute when the solution is again boiled. 
Test for hydrobromic acid as before by blowing across the mouth of the tube. 

Complete decolorization in either part of this test (either in the cold or after heating), if 
unaccompanied by evolution of hydrobromic-acid gas, shows that the compound under exami- 
nation 1s unsaturated; that rs, that it can add bromine. 

The presence of double or triple bondings in hydrocarbons may in the great majority 
of cases be detected by use of the test in the cold only; but there are a few unsaturated 
hydrocarbons like stilbene which require short heating, and in tetraphenylethylene we have 
one which remains unchanged even when heated. Among the unsaturated acids, maleic 
and fumaric acids} also show an exceptional behavior in not decolorizing the tetrachloride 
solution after two minutes’ boiling. Some other unsaturated acids, like aconitic, do not 
decolorize the solution until it has been heated, but the number of such species is not 
large. 

Decolorization in either part of the test when accompanied by a copious evolution of hydro= 
bromic acid always indicates substitution; but since addition may, or may not, have taken place 
at the same time, satisfactory inferences as to the existence of unsaturation in such cases can 


* Carbon tetrachloride is given the preference as the solvent, because bromine solutions pre- 
pared by its use may be kept for weeks without spoiling; because such solutions do not entirely 
lose their orange-yellow color on heating unless boiled for more than twice the time prescribed 
in the test procedure; and because the tetrachloride is such a poor solvent for hydrobromic 
acid that the gas escapes as soon as formed, and thus is easily detected by the fumes 

+ Fumaric or maleic acids will, however, decolorize hot bromine water. (Bromine water is 
as a rule a very unsatisfactory substitute for the carbon tetrachloride reagent, since it is fre- 
quently decolorized by acting as an oxidizing agent, holds back hydrobromic acid, and loses 
its color rather quickly on boiling.) 


195 


196 SEMI-SPECIFIC TESTS FOR SPECIES OF GENUS IX. 


not be drawn. The appearance of scanty traces of hydrobromic acid towards the end of 
an experiment in which a considerable quantity of bromine has been consumed, may, 
however, be due to minor secondary reactions and may be disregarded. 

In the heat, the number of compounds in Order 1 that are attacked by the treatment 
with bromine is greatly increased. The saturated hydrocarbons of the marsh-gas series, 
(CrnHn+,), with unbranched carbon skeletons, and the members of the acetic-acid series, 
(CrH2»O,), are conspicuous examples of compounds unaffected under these circumstances. 
Some paraffin hydrocarbons like diisoamyl with branched carbon skeletons are, on the 
contrary, quite readily attacked in the heat, although not in the cold. Many of the aromatic 
hydrocarbons like mesitylene and anthracene are so easily substituted that decolorization 
occurs within a fraction of a minute in the cold; but pure benzene is so comparatively 

unreactive that it does not cause decolorization within the two minutes’ limit on boiling. 

Most phenols, and many aldehydes and ketones, cause decolorization cold within a 
few seconds. Whenever decolorization takes place readily in consequence of addition or 
substitution in a homogeneous compound, if the experiment is continued after the first 
disappearance of color, it will be found that the quantity of bromine eventually consumed 
will be at least several times greater than what was added at the beginning of the experiment. 


go2. Action of Fuming Sulphuric Acid. 


Support a three-inch test-tube containing 1 cc. of fuming sulphuric acid (sp. gr. 1.89) 
by means of a small clamp in a nearly vertical position, but so that it shall be slightly 
inclined away from the operator. Drop in slowly from a medicine-dropper about five 
drops of the compound. If there are no immediate signs of solution or chemical action, shake 
the mixture cautiously for about one minute. Then allow to stand for a short time, and 
notice whether the compound added separates apparently unchanged as an upper layer. 

If the substance does not dissolve, if heat is not evolved, and if the mixture does not be- 
come strongly discolored, the compound, if a liquid species of Genus IX, with a specific grav- 
ity less than 0.85 at 20°,/4°, may belong to Section 1 (the paraffin section) of Division B. 


903. Action of Fuming Nitric Acid. 


[This test is dangerous unless performed cautiously as directed !] 

In a three-inch test-tube, supported as in Test 902, place 1 cc. of fuming nitric acid of 
specific gravity 1.48. Then add from a medicine-dropper, held at arm’s length, a single drop 
of the compound to be tested. A violent reaction often ensues, and there may be a slight 
explosion, or the substance may even ignite. If there are no signs of action, cautiously 
add a few more drops of the substance, and shake gently. 

If the substance is a liquid species of Genus IX with a specific gravity at 20°,74° 
less than 0.85, and does not dissolve in the acid, and is not attacked by it (as will be in- 
dicated by absence of sputtering and evolution of heat, and by the non-appearance of 
a copious disengagement of red nitrous fumes), it is to be sought for in Section 1 (the 
paraffin section) of Division B.* It is improbable that any of the Species of Section 2 
remains entirely unchanged after such treatment. 

The liquid paraffins, although they are unattacked, and do not dissolve, always dissolve 
oxides of nitrogen so as to acquire a color much like that of the nitric acid. The presence 
of two layers after shaking may, therefore, be easily overlooked in a hasty observation. 


904. Colorations with Aluminium Chloride. 


Drop a hard lump of sublimed aluminium chloride weighing about 0.2-0.3 grm. into a 
clean 6-8-inch test-tube that has just been taken from a hot drying oven. Stopper the 
tube loosely. Hold it in a nearly horizontal position, and by means of a small flame placed 


* The tertiary paraffin diisopropyl is said to be violently attacked by cold nitric acid of 
specific gravity 1.52. 


: 
: 
| 
E 
j 





SEMI-SPECIFIC TESTS FOR SPECIES OF GENUS IX. 197 


under one end slowly sublime the chloride until it forms a thin light-yellow coating cov- 
ering a considerable portion of the glass surface. Allow to cool. Drop in 0.5jcc. of a solution 
containing 0.05 grm. of the hydrocarbon dissolved in 2.5 cc. of chloroform. Stopper the tube 
tightly. Lay it on its side upon a sheet of white paper that rests upon and partly covers the 
color standard. Then roll it back and forth so that the solution shall flow over and wet all 
parts of the sublimate. Observe the color after a few seconds, and again after 15-20 minutes. 

Most aromatic hydrocarbons give colorations when thus treated. The colors are often 
very intense, and sometimes admit of employment as minor preliminary or confirmatory 
tests; but since the hue may be much modified by the presence of small quantities of impuri- 
ties, too great importance ought not to be attached to the indications obtained by their use. 

The initial colorations given by the liquid homologues of benzene approximate orange; 
e.g. pseudocumene, RO; m-xylene, O; benzene, OY (after five minutes). After standing 
fifteen minutes these colors will either remain unchanged, or will change by about one hue 
of the standard in the direction of the red end of the spectrum. The initial coloration with 
diphenylmethane and triphenylmethane is YO, darkening within a few minutes to YOT1; 
with anthracene it is OYS2-YS2. 

Initial colorations of great intensity which persist unchanged for more than twenty 
minutes and approximate blue, are given by several important solid hydrocarbons; e.g. 
blue (B), by diphenyl; blue to green-blue (GB-B), by phenanthrene; and blue-green (BG), 
by naphthalene. 


905. Oxidation of Side Chains. 


The oxidation of the side chains in aromatic hydrocarbons to carboxyl groups by hot 
aqueous solutions of potassium permanganate, chromic acid, or nitric acid, has been em- 
ployed in determining the constitution of many species of Genus IX. The most serious 
difficulty encountered in adapting these methods for use as practical specific tests arises 
from the extreme insolubility of all hydrocarbons in aqueous solutions. This renders the 
oxidations very slow. During the oxidation period—which is seldom less than several 
hours—the oxidation product, which is itself never entirely stable, is exposed to the de- 
structive action of the oxidant. Hence the yield, which even under favorable circum- 
stances falls much under the theoretical, is often very poor indeed. Hydrocarbons which 
are themselves stable, but give unstable oxidation products, are therefore the most difficult 
to treat successfully. Whenever it is suggested in the tables that some particular oxidant 
may be used in the identification of a hydrocarbon, it does not always follow that the 
oxidant mentioned is the best that could have been selected for the purpose, or that the 
yield will be good, but merely that the product named has been obtained by its use. It 
should also be understood that the following general directions are given as suggestions 
rather than mandatory procedures; and that what is said refers more especially to aro- 
matic hydrocarbons having one or two side chains. 

1. (Oxidations with Potassium Permanganate.)—The oxidation with permanganate, 
when applicable, will usually be preferred to either of the other methods. The reagent is 
a neutral aqueous solution containing 61.6 grms. of potassium permanganate to the 
liter. In organic oxidations it is said to be reduced according to the equation 


2KMn0, +2H,0=2Mn0,.cAq. +2KOH +30. 


1 cc. of the solution accordingly contains 0.01 grm. of “available oxygen,” and the alkali 
liberated is sufficient to combine with the full quantity of organic acid and carbon 
dioxide that will be produced in any ordinary oxidation. The iatter fact makes it possible 
to perform these oxidations in closed vessels, and thus avoid the violent bumping that 
is one of the greatest objections to the use of permanganate when the oxidation is performed 
by boiling in flasks. 


198 SEMI-SPECIFIC TESTS FOR SPECIES OF GENUS IX. 


Calculate by aid of the equation given above how much permanganate solution will 
be theoretically needed to produce the desired effect, and place it in a strong wide flask or 
bottle of about one-liter capacity. If, as will sometimes happen, the hydrocarbon is lighter 
than water, and a liquid, the extended contact surface presented by the permanganate 
solution, which will be spread out in rather a thin layer, will do much to accelerate the 
reaction. When the oxidation product expected is benzoic, isophthalic, or terephthalic 
acid, about 1 grm. of the hydrocarbon should be enough for an experiment. 

Suspend the bottle by a wire, so that the lower part will be immersed in a boiling 
water-bath; and, as soon as the air within has been expanded by the heat, and the hydro- 
carbon introduced, stopper tightly to prevent loss of substance by volatilization. Then 
heat until the red color of the permanganate is seen to have completely disappeared. This 
may require from two to eight hours, and some of the hydrocarbon will always remain 
unattacked. Separate the colorless alkaline solution from the bulky brown precipitate of 
hydrated manganese oxide by filtration. LEvaporate to a small volume. Filter if neces- 
sary,and cool. Acidify the solution with a moderate excess of hydrochloric acid, and shake 
vigorously. Benzoic, isophthalic, and terephthalic acid will precipitate at this point. 
The two former may then be identified by their melting-points and specific tests, after 
a single crystallization from boiling water; the latter after being well washed with water. 
Phthalic acid being comparatively easily oxidized by hot permanganate, will not be 
detected, unless the hydrocarbon is one that oxidizes quite rapidly. The loss of benzoic 
acid in long-continued oxidations is also large, though less serious. In an oxidation of 
1 grm. of ethylbenzene requiring six hours, the yield of pure benzoic acid was 0.20 
erm. Benzoic acid is easily separated from any of the phthalic acids by treatment with 
chloroform, in which it is very soluble. 

2. (Oxidations with Chromic-acid Mixture.)\—Boil the hydrocarbon in a round-bot- 
tomed flask containing ebullator tubes (cf. p. 223) with the quantity of chromic-acid 
mixture theoretically required to produce the desired effect, until the chromic acid is 
completely reduced. The apparatus, chromic-acid mixture, and general procedure for 
the oxidation are the same as have been more fully described in Test 702 for the oxidation 
of ketones and alcohols, except that longer heating will be necessary. As the action of hot 
chromic acid on most of the aromatic acidsis even more destructive than that of permanga- 
nate, it is advisable to use at least 2 grms. of the hydrocarbon for each experiment, and 
even larger quantities may sometimes be found necessary. Collect the insoluble residue of 
oxidation products, and unchanged hydrocarbon that separates from the well-cooled solu- 
tion, on a small filter. Wash with a little cold water. Dissolve out the aromatic acids by 
boiling with a slight excess of sodium-carbonate solution. Reprecipitate with an excess 
of hydrochloric acid, and identify them by appropriate tests. 

3. (Oxidations with Dilute Nitric Acid.)—Although nitric acid, being a milder oxidant 
than either permanganate or chromic acid, may be successfully employed in some cases in 
which the latter are inapplicable, and is occasionally mentioned in the tables, it has the 
disadvantage of being exceedingly slow in its action, and of giving products which sometimes 
consist largely of nitrosubstitution derivatives whose removal is troublesome. The 
proper procedure depends so much on the properties of the particular hydrocarbon. to 
be oxidized, that in the few instances in which this method is referred to in the tables, 
it will always be best to consult the original literature relating to the subject before pro- 
ceeding to the experiment. The following general statement and suggestions may, how- 
ever, be of some assistance. 

It is best to oxidize at least 2 grms. of the hydrocarbon with a large excess of acid. 
The nitric acid is usually a mixture of one part of concentrated commercial nitric acid 
with three parts of water, though in some cases a stronger acid can be used, shortening the 


SEMI-SPECIFIC TESTS FOR SPECIES OF GENUS IX, 199 


time without causing much substitution.* The time of boiling varies from six to forty- 
eight hours. In general it is best to boil at least eight hours. If it is expected that a 
solid aromatic acid, not volatile with steam, will be formed, the excess of nitric acid should 
be removed by evaporation on a water-bath. The residue is next extracted with boiling 
sodium-carbonate solution, the solution filtered, and the organic acids precipitated from 
the filtrate by a moderate excess of hydrochloric acid. Nitro-acids may then be reduced 
by warming with tin and hydrochloric acid, so as to form soluble hydrochlorides of the 
corresponding amino-acids, which, upon filtration, will pass into the filtrate. Or, if the acid 
sought should also be soluble in dilute hydrochloric acid, it may be separated from the 
amino-acid by crystallization, after precipitating the tin with sulphuretted hydrogen. 


906. Test for Triple-bonding in Compounds Containing the (~C = CH) Group. 


Dilute 1 cc. of ammoniacal cuprous chloride solution,t in a test-tube, with 5 ce. of 
cold water. Add a few drops of the hydrocarbon, if a liquid, and shake. If the hydro- 
carbon is a gas, conduct it directly into the copper solution. Collect the precipitate on a 
filter. Wash with cold water and observe the color. 

The hydrogen atoms in compounds containing the =CH group are usually replace- 
able by copper when thus treated. These copper compounds appear as insoluble floccu- 
lent precipitates, varying in color, according to the body from which they are obtained, 
from a dark brick-red to a greenish yellow. When washed with alcohol and ether and 
dried with proper precautions, they often explode violently when struck a sharp blow or 
when strongly heated. 


907. Saturated Ethers of Division B. 


Drop 1 cc. of the compound slowly into 2 ec. of ice-cold sulphuric acid (sp. gr. 1.84) 
contained in a five-inch test-tube standing in a beaker of ice-water. Without removing the 
test-tube from the ice-water, shake briskly for half a minute or more. Then, after allowing 
to stand for a minute or two, observe whether the compound has dissolved completely to 
a colorless or nearly colorless solution. In case such a solution has been formed, pour it 
slowly into a second test-tube containing 3 cc. of cold water, shaking and cooling mean- 
while, Just as was done during the preparation of the acid solution. If the mixture on 
standing separates into two layers, remove and reject the lower layer, which will consist of 
dilute sulphuric acid, with the aid of along capillary-pointed medicine-dropper. Wash the 
upper layer by shaking with 2 cc. of sodium-carbonate solution. If an emulsion forms, hasten 
the separation into layers by warming. Remove the carbonate solution as before by the 
aid of the dropper, and transfer the organic liquid to a dry three-inch test-tube. Add a 
small fragment of solid potassium carbonate, and heat nearly to boiling to hasten the drying 
action. Then after a few minutes, in order to ascertain whether the product obtained 
is identical with the original substance, determine the boiling-point of the clear dried 


* Thus Fileti (G. 21, I, 5 and 22) used one part of acid to one of water in oxidizing p-propyl- 
isopropylbenzene, obtaining terephthalic acid with only a trace of a nitro-acid. 

+ Ammoniacal Cuprous Chloride Reagent.—This is the reagent used in gas analysis for the 
absorption of carbon monoxide.—It is prepared from an acid cuprous chloride solution as re- 
quired for use. To prepare the acid solution, cover the bottom of a bottle with a layer of pow- 
dered copper oxide 1 cm. deep. Place in the bottle a number of pieces of rather stout copper 
wire, reaching from top to bottom, sufficient to make a bundle an inch in diameter, and fill the 
bottle with common hydrochloric acid of 1.10 sp. gr. Stopper, and allow to stand with occa- 
sional shaking for some days, or until the solution becomes nearly or quite colorless. When 
about to make a test, decant a little of the clear acid solution, and add ammonia to it until 
present in slight excess, i.e., until the mixture has a distinctly ammoniacal odor. The space 
left in the stock bottle after every withdrawal of solution should be immediately filled with 
more bydrochloric acid (1.10 sp. gr.), and the bottle always be kept tightly stoppered to pre- 
vent absorption of oxygen from the air. 


200 SPECIFIC TESTS FOR SPECIES OF GENUS IX. 


liquid by Siwoloboff’s method. For a more detailed description of the manipulations 
involved in the washing and drying, and in the boiling-point determination, read the 
latter half of paragraph 7. on the identification of soluble alcohols obtained in saponification 
tests (cf. p. 115). 

Any species of Genus IX, Division B, that dissolves in sulphuric acid in this test to a 
clear, nearly colorless solution, which, upon dilution, gives a liquid identical in boiling- 
point with the original substance, is probably the oxide of a saturated hydrocarbon radi- 
cal or, possibly, an ‘‘ unsaponifiable ester.’ Unsaturated ethers and unsaturated hydro- 
carbons may also dissolve completely in the cold acid, or may be entirely decomposed by 
the reagent; but when a clear solution does result, dilution with water can not be expected 
to yield the original substance. Saturated hydrocarbons, even the aromatic ones, do not 
dissolve in the cold acid to any considerable extent. 


giz. Acenaphthene. (Properties tabulated on p. 177.) 


Dissolve 0.05 grm. of the hydrocarbon and 0.10 grm. of picric acid in 2.5 ec. of boiling 
95 per cent alcohol in a dry test-tube. Allow the solution to cool down to the temperature 
of the laboratory gradually. Acenaphthene under these conditions yields a beautifully 
crystallized orange-colored picric-acid compound, C,,H,,.C,H,(NO,),0, whose slender 
flat needles shoot from the bottom of the tube to the surface of the solution. Collect on 
a small filter, and wash with 3 cc. of cold alcohol. Dry for fifteen minutes on a piece of 
porous tile at 100°, and determine the melting-point. 

The color of the dry crystals is nearly the orange of the color standard (O-YO). They 
melt at 161°-162° (uncor.). 


g12. Anthracene. (Properties tabulated on p. 180.) 


Place in a six-inch test-tube 0.05 grm. of the hydrocarbon, 1.5 grms. of chromic acid 
(CrO,), 4 cc. of glacial acetic acid, and 1 cc.of water. Support the tube by a clamp so 
that its lower end shall rest in a circular perforation in a piece of asbestos board arranged 
as in Test 312-2, and boil for ten minutes over a small flame, so gently that the vapors shall 
all condense on the sides of the tube. Pour into 20 cc. of cold water. Collect the floc- 
culent precipitate on a filter. Wash thoroughly with much water, and finally with 5 ce. 
of cold alcohol. Transfer the precipitate to a dry test-tube and boil with 10 ce. of strong 
alcohol. Cool. Collect the nearly white precipitate on a small filter. Wash with 5 cc. of 
cold alcohol. Boil up a second time with 10 cc. of strong alcohol, and again cool. Filter, 
and wash with 5 cc. of cold alcohol. Dry the residue fifteen minutes at 100° on a piece 
of porous tile, and determine the melting-point. 

Anthraquinone, the product obtained in this test, is a pale yellowish compound, crys- 
tallizing from alcohol in minute needles which melt at 279°-280° (uncor.). For other 
characteristic properties of anthraquinone see Test 1011. 


913. Benzene. (Properties tabulated on p. 189.) 


Mix in a dry test-tube three drops of the hydrocarbon, 1 ce. of nitric acid (sp. gr. 
1.42), and 1 cc. of sulphuric acid (sp. gr. 1.84). Heat the mixture until it begins to boil, 
and maintain it at this temperature for half a minute. Then pour slowly into 10 cc. of 
cold water. Cool quickly. Shake. Collect the bulky flocculent precipitate on a small 
filter, and wash until the washings are no longer colored. Dissolve in 8 cc. of boiling dilute 
alcohol (1:1). Allow to stand until the solution has assumed the room temperature. 
The liquid will become filled with long, fine, nearly white needles of m-dinitrobenzene. 
Collect on a small filter. Wash with 5 cc. of cold dilute alcohol (1:1). Drain on a 
piece of porous tile and dry fifteen minutes at 50°. 

The dinitrobenzene formed in this test melts at 89°-89.5° (uncor.). 


SPECIFIC TESTS FOR SPECIES OF GENUS IX. 201 


914. Mesitylene. (Properties tabulated on p. 190.) 


Allow one drop of the hydrocarbon to fall into a mixture of 2 cc. of sulphuric acid 
(sp. gr. 1.84) and 1 cc. of fuming nitric acid (sp. gr. 1.48) contained in a dry test-tube. 
Shake, and then boil very gently for one minute over a small flame. Break up any hard 
lumps that may form with a stirring-rod, and pour into 10-12 cc. of cold water. Collect 
the solid nitro-compound on a very small filter and wash well with cold water. Then wash 
once with 5 cc. of cold strong alcohol. Transfer to a test-tube and boil gently with 15 ce. 
of 95 per cent alcohol (*) until all dissolves. (The compound dissolves quite slowly.) 
Allow to cool. Shake vigorously. Collect the crystalline precipitate in the point of a 
very small filter. Wash with 5 cc. of cold 95 per cent alcohol (**). Drain on a piece of 
porous tile; dry for fifteen minutes at 100°, and determine the melting-point. 

The product in this test, trinitromesitylene, is obtained in the form of minute colorless 
needles melting at 235° (uncor.). 


915. Naphthalene. (Properties tabulated on p. 176.) 


Dissolve 0.05 grm. of the hydrocarbon and 0.10 grm. of picric acid in 2 cc. of boiling 
95 per cent alcohol. Allow the solution to cool gradually. Collect the long, hair-like 
yellow (Y-YT1) needles of the picric-acid compound, C,,H,.C,H,(NO,),0, on a small filter, 
and wash with 1 cc. of strong alcohol. After draining, transfer to a piece of porous tile, 
and press out adhering mother-liquor. Form the crystals into a little mound on a dry part 
of the tile; rinse them off with 5-10 drops of strong alcohol. Repeat the washing with 
alcohol twice more in the same manner, pressing out the adhering alcohol on a dry part of 
the tile each time with a small spatula. Spread out the crystals on a bit of dry tile and 
dry for 15-20 minutes at 50°. Then determine the melting-point. 

The picric-acid compound of naphthalene, thus purified, melts at 150.5° (uncor.). 
(Long-continued drying at a high temperature is inadmissible since it causes a gradual 
loss of naphthalene.) 


916. Phenanthrene. (Properties tabulated on p. 177.) 


Dissolve 0.10 grm. of the hydrocarbon and 0.20 grm. of picric acid in 5.0 ce. of boil- 
ing 95 per cent alcohol. Allow to stand until quite cold. The picric-acid derivative of 
phenanthrene that forms separates in crystals. Collect on a filter, and allow to drain 
well without washing. Transfer to a piece of porous tile to absorb the last of the mother- 
liquor. Redissolve in 1 ce. of boiling alcohol. Allow to cool slowly as before. Collect 
the crystals on a piece of tile to absorb the mother-liquor, and wash with five drops of 
strong alcohol. When the alcohol has nearly all disappeared, place on a fresh piece of 
tile; dry fifteen minutes at 100°, and determine the melting-point. 

The picric-acid compound of phenanthrene, C,,H,).C,H;(NO,),.0, obtained in this 
test, forms long, hair-like needles which are orange-yellow (OY) when dry, and melt at 
143° (uncor.). 


917. Pseudocumene. (Properties tabulated on p. 190.) 


Nitrate two drops of the hydrocarbon by the procedure of Test 914 for mesitylene. 
Do not increase the quantities of acids and solvents prescribed, but follow the directions 
given literally, except that more than usual care must be taken not to overheat during 
nitration. During the operation the test-tube should be held at some distance above the 
flame, and the heating should be interrupted before the expiration of the minute if the 
mixture show signs of darkening, or if a sublimate should begin to appear on the sides of 
the tube. 
_ The trinitro-pseudocumene formed in this test is a nearly white crystalline compound 
melting at 184° (uncor. . 


202 SPECIFIC TESTS FOR SPECIES OF GENUS IX, 


918. Toluene. (Properties tabulated on p. 189.) 


Dissolve three drops of the hydrocarbon in 1.5 ec. of the strongest fuming nitric acid. 
Then add at once, without cooling, 1.5 ce. of fuming sulphuric acid (concentrated sulphuric 
acid containing in solution about 10 per cent of sulphuric anhydride—the same reagent 
that is used for Test 902). After half a minute pour the mixture into 10 ce. of cold water 
in a test-tube. Cool well with running water. Close the tube with the thumb and shake 
vigorously and persistently until the nitro-compound separates in yellowish-white flocks, 
leaving the solution clear. 

Collect the precipitate on a very small filter and wash with cold water. Dissolve in 
8 ec. of boiling 50 per cent alcohol. Cool in running water. Shake vigorously. Filter. 
Wash the precipitate with 5 cc. of cold 50 per cent alcohol. Redissolve the washed pre- 
cipitate a second time in 8 cc. of boiling 50 per cent alcohol. Cool. Shake. Wash with 
5 ce. of 50 per cent alcohol. Dry, and determine the melting-point. 

2, 4-Dinitrotoluene, the product in this test, is a nearly white precipitate of crystal- 
line structure melting at 70°-71° (uncor.). (If the solution, in making the last crystalliza- 
tion, is allowed to cool slowly, the compound will separate out in the form of delicate white 
needles.) 


gI9. m-Xylene. (Properties tabulated on p. 189.) 


Nitrate two drops of the hydrocarbon by the procedure of Test 914 for mesitylene 
Do not increase the quantities of acids or solvents prescribed, but follow the directions 
given literally in every detail, except that the precipitate referred to at the point marked 
by the double asterisk (**) should receive one additional crystallization from 10 ce. of 
boiling 95 per cent alcohol before being dried. 

The trinitro-m-aylene formed in this test is a nearly white crystalline compound melt- 
ing at 181°-181.5° (uncor.). 


920. p-Xylene. (Properties tabulated on p. 189.) 


Nitrate two drops of the hydrocarbon by the procedure of Test 914 for mesitylene. 
Do not increase the quantities of acids or solvents prescribed, but follow the directions 
given literally in every detail, except that the quantity of 95 per cent alcohol used in erystal- 
lizing at the point marked by the single asterisk (*) should be reduced from 15 ce. to 5 ee. 

The trinitro-p-xylene formed in this test is a nearly white crystalline compound melt- 
ing at 138.5°-139° (uncor.). 


921. o-Xylene. (Properties tabulated on p. 189.) 


This hydrocarbon is easily distinguished from the meta and para compounds by the 
fact that when nitrated by the procedure prescribed in Tests 919 and 920, it gives an oily 
instead of a solid high-melting nitro-derivative. The following test may also be applied. 

Sulphonate 0.25 ce. of the hydrocarbon by persistently shaking in a test-tube with 
1 cc. of sulphuric acid (sp. gr. 1.84). During the shaking the tube should be gently warmed 
from time to time by dipping it for a second or two into boiling water. When the hydro- 
carbon has all dissolved (this will require 3-5 minutes), cool, and pour slowly into 10 cc. of 
a saturated solution of common salt. Cool well, and shake vigorously. The mixture will 
soon become pasty from the separation of a heavy precipitate of sodium o-xylenesulphonate. 
Filter, and wash with 10 cc. of a cold saturated salt solution. Press on a tile, and dry 10 
minutes at 125°. Crush. 

Mix 4 parts by weight of phosphorus pentachloride with 3 parts of the dry sulpho- 
nate in a test-tube, and heat for 10 minutes at about 100°. Cool, and pour in 5 ce. of ice-cold 
water. Shake. Allow to settle. Decant the water through a wet filter. Wash again 


SPECIFIC TESTS FOR SPECIES OF GENUS IX. 203 


by shaking with 5 cc. of cold water, followed by decantation. Return any precipitate 
that may have collected on the filter to the test-tube. Add 2 cc. of the most concentrated 
ammonia. Boil gently until the ammonia odor has almost disappeared. Dilute with 
10 ce. of water. Heat to boiling. Filter hot. Cool the filtrate well with ice water. Shake 
vigorously, and collect the precipitate of the sulphonamide on a small filter. Wash with 
5 ce. of cold water. Redissolve in 5 ce. of boiling water, and cool. Shake, filter, and wash 
as before. Repeat these operations twice more. Then dry for 15 minutes at 110° and 
determine the melting-point. 

o-X ylenesulphonamide, the product of this test, crystallizes in pearly-white scales 
which melt at 143.5°-144°, 


CHAPTER XII. 
S.U'B'O RD Ee Rael 


THE COLORED COMPOUNDS OF ORDER I. 


(Containing Carbon, Hydrogen, and Oxygen.) 


THE CONTENTS OF SUBORDER II ARE INDICATED BY THE TITLE ‘‘ COLORED COM- 
POUNDS.” ANY CAREFULLY PURIFIED SOLID SPECIES OF ORDER I WHOSE 
COLOR EXCEEDS TINT 3 OF THE COLOR STANDARD (CF. PAGE 281) IN SATU- 
RATION, OR ANY YELLOW LIQUID SPECIES WHOSE COLOR WHEN VIEWED IN 
A LAYER 1 CM. THICK AGAINST A WHITE BACKGROUND IS MORE SATURATED 
THAN YT1 OF THE STANDARD, WILL BE CONSIDERED COLORED. 


A very faint tinge of straw-yellow, caused by traces of impurities or decom- 
position products so small as to have no appreciable effect on the general chemical 
behavior of the substance, is often observed in specimens of compounds belonging 
to Suborder I. In doubtful cases the attempt should be made to decolorize such 
substances by boiling their solutions with purified bone-black. Compounds with 
colors less saturated than the tints of Series 3 of the color standard are described 
in Suborder I with the colorless compounds, but also sometimes receive mention 
in Suborder II. 

Subdivisions of Suborder II.—The species described in Suborder II are arranged 
in two divisions, A for solids, and B for liquids; but are not numerous enough to 
yequire further subdivision into genera. They are all either ketones, quinones, or 
phenols. 

The solid species are grouped in two sections. The arrangement in Section 1 
is based upon melting-point, as 1s customary for solids in other parts of the work. 
Section 2 is virtually an appendix to Section 1, added to provide for the partial 
identification of certain important bodies, dyes, and acidimetric indicators, which 
have the common property of giving intensely colored solutions in alkali, but which 
fuse with so much decomposition, or at such high temperatures, or which are so 
difficult to isolate in a state of perfect purity, that their melting-points are unknown 
or have little practical significance. Some of these bodies are not met with except 
in the form of moist pastes and amorphous powders of rather variable compo- 
sition, and are only admitted to the tables as compounds by courtesy because of 
the interest attaching to them as colors. 

The arrangement of species in Section 2 is dependent on the color of the solution 
of the substance in dilute aqueous alkali, as is more fully explained on page 212. 
To make the color comparison, dissolve a few milligrams of the finely powdered sub- 
stance by shaking in a test-tube with 5 cc. of 1 per cent cold sodium-hydroxide 
solution; and then dilute, if necessary, with water, until the mixture when held 
before a white background shows a depth of color that approaches either the normal 
tone, or the first tint of that hue of the standard which the color of the solution 
most closely resembles. The comparison should be made quickly, as many of the 
solutions absorb oxygen from the air, or change rapidly in both hue and tone on 


standing. 
204 


SUBORDER II, 


COMPOUNDS CONTAINING C, H, AND O [ORDER I]. 
COLORED COMPOUNDS. 


DIVISION A, SECTION 1,—SOLID SPECIES OF DETERMINED 


MELTING-POINT. 





Melting-point 
CORDE 


28 
41 


45-5 


55 


57-8 
59-60 


68 
68-9 


69-70 


ral 


72-3 
83 -5-4 


90 


ee ch Pa ee ee eee ena 


COLORED COMPOUNDS.—Solid Species of Determined Melting-point. 


+ Phoron, C,H,,0.—B. p. 198-5°.—Pale-yellow cryst.—Cf. VII, A, p. 136. 

Benzfuril, Ph.CO.CO.C,H,0.—Fine yellow ndl. fr. h. dil. ale-—Volatile undec.— 
S. alkalies giving benzfurilic ac. (dec. 108°).—25 pt. c. Br give tetrabromide, 
yellow ndl. fr. alc., m. p. 127°-8°. 

t+ Thymoquinone, (Me).(Me,CH).0O..C,H.(1, 4, 2,5).—B. p. 232°.—Orange-yel- 
low (OY) tbl. v. d. s. aq.; e. s. ale. or eth.—Odor sharp like quinone, but 
also like thymol!—S. without decomposition in c. cone. H,SO, or HNO,.-— 
For characteristic color reactions cf. B. 18, 3196.—Heat 0-1 grm w. 5 cc. 
aq. and 0-2 grm. Br for $ hr. on boiling water-bath. Wash the red oil with 
c. aq. until it is yellow and crystalline. Recryst. twice fr. 2 cc. h. alc. (add- 
ing a little eth. if oil should not crystallize readily). Gives dibromide, yel- 
low lfts., m. p. 73°. 

1, 2-Dimethylquinone(3, 6), Me,.C,H,.0,.— Sbl. in yellow ndl., d. s. aq.; as 
alc. or eth. 

tT Benzylideneacetophenone.— Pale yellowish pr.—Cf. VII, A, p. 137. 

Dioxybenzophenone, (C,H,.0H),.CO.—B. p. 330°—-40° d.—Light-yellow ndl. fr. 
lgr.—Alm. i. aq.; v. s. alc. or eth.; s. K,CO,; but ppt’d by CO,.—Sol. in dil. 
alc. colored brown-red by FeCl,.—Warming w. conc. H,SO, or boiling w 
KOH sol. gives o-benzophenone oxide, ndl. fr. alc., m. p. 173°-4°, v. d.s. c. aq, 

Methyl Cinnamenylvinyl Ketone, C,,H,,O.—Cf. VI, A, p. 137. 

Toluquinone(2, 5), Me.C,H;.0,,—Sbl. in rhombic-yellow lft., d. s. c. aq.; v.s. 
alc. or eth.—Odor pungent, quinone-like !—Aq. sol. is colored brown-red by 
alkalies —Reduced by SO, to hydrotoluquinone, v. s. aq.; pearly lft. fr. bz.; 
m. p. 124°. 

Diphenylpropanetrione, (PhCO),.CO.—B. p. 247° (60 mm.).—Golden-yellow ndl. 
fr. lgr.; e. s. ale—Very hygroscopic.—Sapon. by NaOH gives benzoic and 
mandelic acids, benzoin, and CO,.—2 pt. boiled w. 5 pt. aniline and 10 pt. 
alc. give a dianil, yellow pyramids fr. bz., m. p. 148°. 

Phenoquinone, C,H,0,.2C,H,O.—Fine red ndl. w. green reflections !—S. c. aq. ; 
e. s. alc. or eth.; s. lgr. (dif. fr. quinone and quinhydrone).—The red crystals 
become blue-black upon addition of alkali.—Reduced to hydroquinone (Test 
411) by SO. 

1, 3-Dimethylquinone(2, 5), Me,.C,H,.0,,—Yellow ndl. 

Diphenylene Ketone, (C,H,)..CO.—B. p. 341-5°.—Large yellow tbl. fr. B16.5 1: 
aq.; v. s. ale. or eth.—Slowly oxid. by alkaline KMnO, to phthalic ac.— 
Oxime, m. p. 195°.—Well-cooled, fuming HNO, gives yellow nitro-comp. 
which sbl. easily, is d. s. c. alc., and melts at 220°.—Fusion w. KOH gives 
phenylbenzoic ac. 

Pseudodiphenylene Ketone, C,,H,0.—Dark-red cryst. fr. eth.—C. fuming HN Os . 
gives dinitro-comp., ndl. fr. h. glacial Ac; i. ale.; m. p. 310°.—Boiled w. dil. 
ale. quickly gives diphenylene ketone (cf. above). 

Acetonephenanthrenequinone, C,,H,,0;.—Thin pale-yellow tbl. fr. eth.; i. aq.— 
Phenanthrenequinone separates upon boiling w. KOH sol. 

Retene Ketone, C,,H,,0.—Vitreous sulphur-yellow cryst. ; vol. w. st.; e. s. ale. 
or eth.; i. NaHSO,.—Combines w. phenylhydrazine, but not w. hydroxyl- 
amine.—Ignition w. Zn dust gives retenefluorene. 


— 


205 


206 


Melting-point 
(C8), 





92-3 


95 


98 


102-3 


103 


103 


103-4 


104 


106 


109-10 


111 


112-2-5 


115-7 


d. 115-20 


120-5 


125 
125 





SUBORDER II, DIV. A, SECT. 1, 


(ORDER I.) 


COLORED COMPOUNDS.—Solid Species of Determined Melting-point 


Acenaphthylene, C,,H,.—Golden-yellow cryst.—Cf. LX, A. 

+ Benzil, Ph.cO.CO.Ph.—B. p. 346°-8° c.—Fine pale-yellow (YT2) ndl., i. aq.; 
e. s. alc. or eth.—Dissolve 4 pt. in x’s abs. alc.; add 1 pt. solid KOH and 
boil down in porcelain dish. An intense violet color (VR) appears, but 
disappears on continued boiling !—Sapon. w. NaOH gives benzilic ac. (quan- 
titative).—Gives oximes. 

Benzocotoin, (OH)(COPh)(OMe),.C,H,.—Pale-yellow pr. fr. alc.; e. s. eth.; s. 
dil., but i. conc. NaOH.—PbAc, gives yellow ppt. w. NH,OH sol.—Sol. gives 
dark-brown color w. FeCl,. 


Cinnamyleneacetophenone, C,,H,,0.—Golden ndl. fr. ale-—Colored cherry-red 
by conc, H,SO,.—Oxime, m. p. 131°. 

Oxy-m-xyloquinone, Me,.C,H.(OH),.0,.—Orange-red ndl., v. vol. w. st.—Sbl. 
in yellow ndl.—Odor like benzoquinone !—S. h. aq.; sol. colored red-violet 
by alkalies, even by CaCO,! 


Methyl Oxynaphthyl Ketone, Me.CO.C,,H,.OH.—B. p. 325° sl. d.—Pale-green 
6-sided pr. fr. bz. !—I. aq.; d.s. alc.; s. alkalies, but ppt’d by CO,.—Oxime, 
m. p. 168°-9°. . 

Pipitzahoic Ac., (Perezon), C,;H.,0,.—Golden lft. fr. ale-—Sbl. undec.—S. in 
KOH w. intense purple color.—Ba salt purple and v. d. s. aq.—CO, sepa- 
rates ac. fr. salts. 


Santalin, C,,H,,0,(?).—-Mic. red cryst. or red mass; misc. w. abs. alc. w. blood- 
red color; s. eth.—A weak acid, s. alkalies w. violet color—Ammon. sol. 
gives dark-violet cryst. ppt. w. BaCl,—KOH fusion gives Ac and resorcin 
(cf. Test 418). 


Cinnamylenebenzylideneacetone, C,,H,,0.—Yellow pr. fr ale-——Oxime, yellow 
Ifts., m. p. 127°-8°. 


Phenylnaphthoquinone, Ph.C,,H,;0,.—Golden-yellow ndl. fr. ale.; s. eth.; d. s. 
lgr.—Polymerized quickly by sunlight.—An alc. sol. sat. w. NH, separates a 
comp. (red ndl. s. eth.) on standing, m. p. 174°.—Gives aniline derivative 
fr. h. ale. sol. w. aniline, dark-red ndl., m. p. 158°. 


I, 2, 4, 5-letramethylquinone, Me,.C,.0,.—Sbl. at 100° in golden ndl., d. s. ¢e. 
ler.; v.s. alc. or eth.—Very volatile with steam. 


| Dibenzylideneacetone, (Ph.CH:CH),.CO.— Gives Test VII-1.— Yellow Ift., 
d.s. alc.; s. eth.—S. in conc. H,SO, w. deep orange-red color.—Colored dark 
vermilion by conc. HCl without being dissolved.—Adds Br, in CHCl, sol. to 
form comp. of m., p. 208°-11° d., ndl., v. d. s. ale. or eth. 

+ Benzoquinone, p-C,H,.0,.—Peculiar, sharp irritating odor slightly suggesting 
that of chlorine !—Golden-yellow monoclinic pr. fr. h. aq.; d.s. ¢. aq.; e. 8. 
alc. or eth.; s. h. lgr.—Sbl. easily in golden ndl.—Sol. in alkalies absorbs 
oxygen rapidly, becoming dark-colored.—Identify by Test 1012! 


I, 2-()-Naphthoquinone, C,,H,O,.—Small odorless red ndl. fr. eth., or orange lft. 
fr. bz.—Not vol. w. st. —-Unstable.—Sol. in dil. NaOH is yellow and absorbs 
O rapidly.—Add 14 pt. aniline to a cone. sol. of 1 pt. of the quinone in h. 
alc.; anilinonaphthoquinone separates as red ndl. w. golden to greenish 
reflections, i. aq.; d.s. alc.,m. p 240° (differs from aniline a-naphthoqui- 
none in being s. in cold alkalies) —KMn0O, oxidizes to phthalic ac.—Reduced 
by SO, to corresponding hydroquinone. 


+ Absinthin, C,,H,.0,+ 4H,0.—(Fr. Artemesia absinthium.)—Yellowish (OYT2) 
mic. cryst. fr. alc. w. bitter taste and wormwood odor (sample fr. Merck) !— 
Alm. i. c. aq.; e. s. ale or eth.—Sol. in NaOH is brown-red.—Sol. in H,SO, 
is brownish and then green-blue liq.—Reduces ammon. AgNO,, but not 
Fehling’s sol.—Ale. sol. gives ppt. w. tannic ac. 


Benzohydroquinone, Ph.CO.C,H;.(OH),.—Long yellow ndl. fr. dil. ale.; e. s, 
ale. or eth. 


1, 4-Dimethylquinone(2, 5), (Phloron), Me,.C,H,.0,.—Long golden-yellow ndl. 
fr.alc.; d.s. h. aq. or c. ale-—Sbl. undec.—Reduced by SO, to hydrophloron, 
—Br aq. gives dibrom-derivative, golden lft. fr. h. ale., m. p. 184°.—Aniline 
derivative yellow-green ndl., m. p. 264° (A, 255, 171). 





SUBORDER II, DIV. A, SECT. 1. 207 


(ORDER I.) 





Melting-point 
CGE 


125 


127 


129 


abt. 130 
130-1 


132-5 
133-4 


135 


140 


140 


140-1 


142 


142 
143-4 


143-4 


146-7 


146-8 


COLORED COMPOUNDS.—Solid Species of Determined Melting-point. 


1 1, 4-(a)-Naphthoquinone, C,,H,O,.— Yellow (Y) ndl. w. pungent quinene like 


odor, which is, however, much less intense than that of benzoquinone.—E. 
vol. w. st. (dif. fr. -comp.).—S. ale.; e. s. eth.; d.s. aq.—Sol. in alkali is 
red-brown.—Identify by Test 1013! 

Oxylapachol(a), C,,H,,0,.— Yellow ndl. e. s. alc., eth., or alkalies—AgA + H,O, 
chestnut-brown cryst. ppt. 


| af-Dibenzoylstyrene, Ph.CO.CPh: CH.CO.Ph.—Pale-yellow ndl. (YT2) fr. alc., 
v. d. s. c. alc. or eth.; e. s. h. alc —Odor faint aromatic.—M. p. of nitro 
deriv. 155°. 

Oxypipitzahoic Ac., C,,H,,0,.—Reddish-yellow lft.—Sol. in KOH is violet-red. 

+ Cotoin, MeO.C,H,(OH),.CO.Ph.—(In coto bark.)—Pale-yellow pr. fr. h. aq.— 
Sulphur-yellow (sample fr. Schuchardt YT2) tbl. fr. ale-—Taste sharp and 
biting; dust provokes sneezing.—V. d. s. c. aq.; e. 8. alc., eth., NaOH, or 
Na,CO,, but ppt’d by CO,.—Reduces ammon. AgNO, sol. cold and Fehling’s 
sol. on heating.—In conc. aq. sol. FeCl, gives brown-black ppt. and in alec. 
sol. brown-red color.—Warming w. conc. H,SO, gives benzoic ac. and phloro- 
glucin.—Sol. in ammonia gives yellow amorphous ppt. w. PbAc,.—Yields a 
cryst. oxime. 


Chrysoketone, C,,H,,O.—Silky yellow ndl. or orange-red pr. 

Salicyloresorcin, HO.C,H,.CO.C,H;.(OH),.— Yellow lft. fr. h. ale.—S, h. Na,CO, 
sol., but ppt’d by CO,.—Fusion w. KOH gives resorcin and salicylic ac. 

+ Furoin.— When pure, slightly yellowish; usually buff colored. Sol. in NaOH 
violet-red.—Cf. Genus IV, A. 


+ Hematoxylin, C,,H,,0,+ 3H,0.—Melts w. loss of aq.—Taste sweet !—Colorless 
tetragonal pr. when pure and freshly prepared, but soon changed by sunlight 
to dark red-brown.—D. s. c. aq.; e. s. alc., eth., or h. aq.; s. alkalies and 
alkali carbonates w. intense beautiful purple-red color, changed by acids to a 
clear orange-yellow (OY).—Thin layers of the very intensely colored alkaline 
sol. are V; largely diluted VR and R.—Gives dark color w. FeCl, and finally 
a ppt.—W. alum sol. gives rich RV color, which largely diluted gives VR.— 
Reduces ammon. AgNO; sol. in the cold. 

Lapachol, C,,H,,0;—Small yellow pr. fr. eth. or bz—Sbl. w. much difficulty.— 
S. NaOH or Na,CO, w. red color.—Dissolved by shaking w. 5 pt. conc. H,SO, 
and ppt’d by aq. gives §-lapachon, which cryst. fr. alc. in flat orange-red ndl., 
m. p. 155°-6°.— Readily oxid. to phthalic ac. by HNO, (sp. gr. 1-38). 

j Alizarin Yellow A (Trioxybenzophenone), (HO),.C,H,.CO.Ph.—(Cryst. w. 1 
aq.).—Yellow ndl., d.s. h. aq.; e. s. alc. or eth.; ppt’d fr. Na,CO, sol. by 
CO,.—Sol. in conc. H,SO, yellow.— Warming w. conc. H,SO, gives benzoic ac. 


Pyrene Ketone, C,,H,0.—Golden-yellow tbl. fr. ale—Gives NaHSO, comp.— 
Fuming HNO, dissolves w. deep purple-red color—KMn0O, oxid. to naph- 
thalic ac. 


+ Dicinnamenyl Vinyl Ketone, C,,H,,0.—Golden-yellow ndl. fr. abs. ale.; d. s. 
c. alc. or eth. 


Perezinon, C,,H,,0,.—Pale-yellow ndl. s. ale. or eth—Garnet-red on warming 
with Millon’s reagent. 


2, 4’-Dioxybenzuphenone, (C,H,.0OH),.CO.—Pale-yellow Ift. fr. h. aq.; e. s. ale. 
or eth.; s. alkalies, but ppt’d by CO,.—Fusion w. KOH gives phenol and p- 
oxybenzoic ac. 


1-Oxyxanthone, C,,H,O,.—Clear-yellow ndl. fr. alc.; d.s. h. aq.—Fusion w. KOH 
gives resorcin and salicylic ac.—W. Br in Ac sol. gives dibrom-derivative, 
yellow ndl., m. p. 222°. 


+ Barbaloin, C,,H,,0, (dried at 100°).—(Before drying, yellow ndl., w. xH,O, 
m. p. 70°-80°).—Taste sweetish and then very bitter.—S. 60 pt. aq., 20 pt. 
alc., or 470 pt. eth.; v. s. NaOH to deep orange-red sol.; e. s. acids.—A 
trace of FeCl, gives fine red-violet color w. aq. sol.; more FeCl, gives a green- 
ish black !—Br water added drop by drop w. a pause of 4 min. between each 
addition gives a fine VRT2 color. An x’s of Br immediately changes the 
color to yellow, and then gives a vellow ppt. of tribromaloin.—A little of the 
powder stirred into a drop of HNO, (sp. gr. 1-2) gives a deep carmine-red, 
soon changing to orange. (The carmine color w. nataloin is permanent, but 
is not given at all by socraloin ) 








SUBORDER II, DIV, A, SECT. 1, 


(ORDER I.) 





Melting-point 
(Cosh 


148 


149 


152 


151-4 


156-8d. 


Ay All 


171-2 


170-78 


177 


177 


178 


178(?) or 190 


COLORED COMPOUNDS.—Solid Species of Determined Melting-point. 


Vulpic Ac., C,yH,,0,.—(In Cetraria vulpina.)—Yellow monoclinic lft. fr. ale., v. 
d. s. alc.; e. s. eth.—Heated above 200° gives MeOH and pulvic anhyd.— 
Sapon. by boiling Ba(OH), gives MeOH, oxalic, and a-toluic ac. 


2, 3, 4, 2’-Tetraoxybenzophenone, (OH),.C,H,.CO.C,H,.OH.—Cryst. w. 1H,O in 
greenish-yellow Ift.; e. s. alc. or eth.—W. warm conc. H,SOQ, splits to sali- 
Cylic acs. ete. 

Paracotoin, C,,H,O,.—Pale-yellow lft., d. s. h. aq.; e. s. eth. or h. ale.—S. in 
alkalies, sapon. giving a yellow i. ac., m. p. 108°.—Fusion w. KOH gives 
piperonylic ac.—Br substitutes in c. CHCl, sol. giving comp. cryst. fr. alc., 
m. p. 200°-1°. 

5-a-Oxynaphthoquinone (Juglon), HO.C,,H,;.0,.—Yellowish to brick-red ndl. 
fr. CHCl,.— Begins to darken on heating to abt. 125°.—Somewhat vol. w. 
st.—I. aq.; e. s. ale.; s. conc. H,SO, w. intense blood-red color, s. in very 
dil. NaOH w. purple color, changing to brown.—Boiling w. aq. gives i. green- 
ish-brown powder, s. in alkalies w. deep-violet color.—CuAc, added to ale. 
sol. gives dark-violet mic. pr. w. metallic lustre. 


Euxanthic Ac., C,,H,,O,,.—Straw-yellow ndl., anhydrous when fr. ale.—D. s. ¢. 
alc.; e. s. eth.—PbAe,, yellow gelatinous ppt.—Dist. w. HCl gives furfurol 
(Test 115). 


Furil, C,H,0.CO.CO.C,H,0.—Golden-yellow ndl. alm. i. aq.; d.s. eth. or c. alc.; 
e. s. CHCl,.—Sapon. gives furilic ac. (v. unstable).—E. dec. by conc. HCl.— 
Reduced to furoin by Na amalgam. 


{+ Anthranol.—Cf. Genus IV, A.—Color YT2-YT3. D. s. in alkali w. bright- 
yellow color. 


Diphenylbutanoltrion, Ph.CO.CH(OH).CO.CO.Ph.—Yellow pr.; e. s. alc. or eth. 


Dioxydimethyltriphenylmethane, (Me.C,H,.0H),.CH.Ph.—Pale-yellow ndl. fr. 
dil. alc.; d.s.aq.; e. s. alc. or eth.; e. s. dil. NaOH.—Gradually turns 
red on exposure to air, especially if warmed. Diacetate by boiling w. x’s 
acetic anhyd., yellow ndl. fr. ale., m. p. 94°. 

t+ Quinhydrone, C,H,.0,.C,H,.(OH),.—Dark-green pr. w. metallic lustre, red- 
brown by transmitted light !—Sbl. w. slight dec.—S. h. aq.; e. s. ale. or eth. 
w. yellow color; i. lgr.—Boiled w. aq. splits to quinone and hydroquinone.— 
Reduces ammon. AgNO, sol.—Reduced by SO, to hydroquinone (Test 411), 


6-Phenyl-3-benzoylpyronon, C,,H,,0,— Yellow ndl. fr. ale.; d.s. c. alc., e. s. 
eth.—Boiled w. ale. KOH gives acetophenone, benzoic, and acetic ac.— 
FeCl, gives orange-red color w. alc. sol.—Sol. of NH, salt gives a scarlet-red 
ppt. w. FeCl,—Sol. in conc. H,SO, is olive-green, becoming violet when 
warmed. 


+ Chrysarobin, C,,H,,0,.— Yellow nd. or lft. fr. acetic ac. (sample fr. Merck YS1 
powd.).—Sbl. w. dec. in yellow Ift.—I. aq. or NH,OH; s. in not too dil. 
KOH w. yellow color and green fluorescence.—Air passed through sol. oxid. 
to chrysophanic ac., m. p. 162°.—Ignition w. Zn dust gives methylanthra- 
cene.—Sol. in conc. H,SO, is yellow. 

2-Methylanthraquinone, Me.C,,H,.0,.—Pale-yellow lustrous ndl., s. eth.; v. d. 
s. alce.; s. conc. H,SO, w. blood-red color, changing to violet on heating !— 
Ignition w. Zn dust gives 2-methylanthracene. 

2-Naphthyl-1, 4-Naphthoquinone, C,,H;.C,,H,.0,.—E. s. alc. or bz.; s. conc. 
H,SO, w. indigo-blue color! 

Curcumin, C,,H,,0,.— Yellow or orange-yellow pr.; i. aq.; d. s. ale.—Sol. in 


eth. fluoresces green.—S. alkalies w. intense red-brown color.—Sol. in cone. ° 


H,SO, is fine reddish purple.—Alc. sol. gives bright-red ppt. w. PbAc, sol.— 
Place piece of filter-paper in alc. sol. and evaporate to dryness at 100°. 
Saturate paper w. boracic ac. sol. A red color appears at once or cn evap- 
orating. A drop of NaOH sol. will give series of fine colors, green and pur- 
ple most prominent; HCl will give a red color changed to green and tas 
by x’s of alkali. 

Dioxymethylanthraquinone (Chrysophanic Ac.), C,,H,,0,.—6-sided tbl. fr. bz.; 
golden yellow ndl. fr. ale.; s. eth. or h. ale.; v. d. s. NH,OH or alkaline car- 
bonates; v.s. NaOH; in each case w. deep-red color.—Salts dec. by CO;.— 
Ignition w. Zn dust gives methyl anthracene. 


"a 
a 


SUBORDER II, DIV. A, SECT. 1, 209 


(ORDER I.) 
eo aa COLORED COMPOUNDS.—Solid Species of Determined Melting-point. 
181-2 Fluorenequinone, C,,H,O,.—Yellowish granules fr. bz.—Hot KOH sol. gives 
brown product w. odor like diphenyl. 
185-5 Picylene Ketone, C,,H,,0.—Golden-yellow cryst. powder, e. s. h. bz.—Fusion w 
KXOH gives picenic ac. 
188 Fluoranthenequinone, C,,H,O,.—Small red ndl.; s. ale. or NaHSO, sol.—Quickly 


oxidized to CO, by CrO, mixture (dif. fr. fluorenequinone).—Ignition w. soda- 
lime gives diphenyl. 

187-92c. Sinapic Ac., C,,H,,0,.—Pale-yellow ndl., e. s. h. alc.; i. eth.—Na salt gives red 
ppt. w. FeCl, 

a. 190 Rutin, C,,;H;,0,,+2H,0.—(In leaves of rue: Ruta graveolens.)—Clear yellow 
silky ndl. fr aq.—Loses 2H,O at 150°-60°.—E. s. h. aq.; 1. eth.; s. alkalies, 
—Sol. colored dark green by FeCl,!—Hydrolyzed by boiling w. dil. ac. to 
quercetin and rhamnose. 

191-2 o-Diphenyleneketonecarbonic Ac., C,,H,O;.—Orange-red ndl. fr. dil. alc., alm. 
i. aq.; e. s. eth.—Ignition w. Zn dust gives fluorene. Warmed w. fuming 
HNO, gives nitro ac., m. p. 245°-6°. 

195 Caffeic Ac., C,H;.(OH),.CH: CH.CO,H.—(Cryst. w. $H,O.)—Straw-yellow pr. fr. 
aq.; e. s. ale.—Aq. sol. becomes grass-green w. FeCl, changing to blue or 
violet upon addition of Na,CO,.—Alkaline sols. brown in the air.—Aq. sol. 
reduces h. AgNO, and gives a yellow ppt. w. PbAc,.—Dist. gives pyrocatechin, 
Test 416. 

195-6 a-Usnic Ac., C,,H,,0;,—(Fr. various lichens.)—Sulphur-yellow pr. fr. h. alc.; 
d.s. c. alc. or eth.—Very weak acid.—Salts are yellow.—FeCl, gives a dark 
brownish-red color w. alc. sol. 

197-7-5 Retenequinone, C,,H,,0,.—Flat orange ndl.; s. h. alc.; d.s. h. eth. or lgr.; i. 
c. NaOH; s. conc. H,SO, w. green color !—A drop of ale. KOH added to an 
alc. sol. gives dark Bordeaux-red color which disappears on shaking w. air! 
Upon warming w. exclusion of air, color reappears.—Ignition w. Zn dust 
gives retene, m. p. 94°. 

199-201 Carbousnic Ac., C,,H,,0,—(In lichens.)—Yellow pr. similar in properties to 
a-usnic ac. (cf. m. p. 195°-6°). 

200d. Eupittonic Ac., (MeO),.C,,H.O,.—Hair-like orange ndl. fr. ethyl ale.—Dibasic.— 
The blue solution in NaOH gives blue ppt. of Na salt with x’s alkali which 
changes to green cryst. after 24 hrs. 

200-1 Bithymoquinone, C.,H,,0,.—Long clear yellow silky ndl., not vol. w. st.—V. d. 
s. solvents; i. abs. eth.; s. undec. in h. fuming HNO;.—Dist. gives much 
thymoquinone (cf. p. 205) !—Not reduced by SO,, but gives hydrothymo- 
quinone when dist. fr. Zn dust. 

200-2 Euxanthonic Ac., [C,H;.(OH),],.CO.— Yellow warts or cryst. fr. h. aq., s in KOH 
w. yellow color which darkens rapidly in the air——Red-yellow ppt. w. PbAc, 
sol.—Fusion splits to euxanthone and H,O.—FeCl, gives red color. 


202 Quinacetophenone, Me.CO.C,H,(OH),.—Pale yellow-green cryst.; v. d.s. c¢. aq. 
—Reduces Fehling’s sol.—IeCl, gives transient deep-blue color w. aq. sol. 
202 + Phenanthrenequinone, C,H,.CO.CO.C,H,.—B. p. a. 360°.— Yellow-orange (YO) 


ndl.; sbl. in cryst.; d.s. h. aq.; d. s. alc. or eth.; e. s. h. Ac; e. s. warm 
NaHSO, sol. !—Ignition w. Zn dust gives phenanthrene; w. soda-lime, di- 
phenyl.—Identify by Test 1014! 
206d. a-Anthracenecarbonic Ac., C,,H,,O,.—Cf. III, A, 2. 

202-19d. Scoparin, MeO.C,H;.(OH).C,,;H,O;.(OH) 5+5H,0.—(In Spartium scoparium.)— 
Small clear yellow cryst. fr. 70% ale.; v. d. 8. ¢. aq.; e. s. h. aq.; i. eth.; 
e. s. NaOH or Na,CO, giving greenish-yellow sol.—Bleaching powder colors 
dark red —HNO, gives picric ac.—Fusion w. KOH gives phloroglucin, va- 
nillic, protocatechuic, and acetic acids. 


211-12 Isoanthraquinone, C,,H,O,.—Pale-yellow ndl.—Fusion w. KOH gives blue mass. 
—More s. in H,SO, than anthraquinone. 
214-15 Pulvic Ac., C,,.H,,0,.—Orange pr. fr. ale. which effloresce to orange powder’ s. 


aq., eth., CHCl,, or bz.—Adds Br, and is oxid. by alkaline KMnO,. 





ee 


210 


SUBORDER II, DIV, A, SECT. 1. 


(ORDER I.) 





Melting-point 
(CON), 





240c. 


abt. 250 


253-6d. 


256 


261 


262-3 





COLORED COMPOUNDS.—Solid Species of Determined Melting-point. 





{ Piperic Ac., CH,.0,.C,H,;.CH: C,H,: CH.CO,H(3, 4, 1).—Pale-yellow (YT2) ndl., 
alm. i. aq.; s.h. ale. or eth.—f The sol. in dil. Na,CO, when gently oxid. by 
warming on a watch-glass w. a few drops of KMnO, sol. emits the delicate 
heliotrope aroma of piperonal !—BaaA,, i. ¢. aq. 

Purpurin-1-carbonic Ac., C,,H,(OH),0,.CO,H.—Red Ift., i. c. aq. or ale.; d. s, 
h. CHCl,.—Sol. in Na,CO, is orange-colored.—Boiling w. aq. or alc. gives 
CO, and purpurin. 

a-Dioxyanthracene, C,,H,,0,.—Yellow lft. or ndl., v. s. ale; the yellow sol, 
fluoresces strongly blue.—FeCl, or Br gives blue-green color w. alc. sol. 

Oxylepidene (‘‘ Needle-shaped”’), C,,H,,0,.—Yellow ndl., i. aq.; d.s. h. ale; 
alm, i. eth. 

Diphenyleneketonecarbonic Ac., CO.C,,H;.CO,H.—Yellow ndl. fr. ale.; i. aq.; 
s. conc. H,SO, w. yellow color.—Gives oxime, m. p. 263°.—AgaA yellow ppt. 

Purpurinxanthinecarbonic Ac., C,,H,(OH),O,.CO,H.—Golden Ift. fr. glacial Ac, 
s. eth. or h. aq.; s. in NaOH w. red color, or in conc. H,SO, w. intense yellow 
color.—Dec. above m. p. 

2-Oxyxanthone, C,,H,0,.— Yellowish ndl. fr. dil. ale-—Acetyl deriv., m. p. 161°, 

Oxylepidene (‘‘ Octahedral’’), C,,H,,O,.— Yellowish octahedra fr. h. Ac, alm. i. 
alc.; i. h. alcoholic KOH.—Heated nearly to boiling gives isomer, s. alc., w. 
Miipelso., 

Chrysoquinone, C,H,.CO.CO.C,,H,.—Orange-red ndl.; s. h. ale.; v. d. s. eth.; 
s. in cold H,SO, w. corn-flower-blue color, ppt’d by aq. (delicate). Sbl. in 
red ndl. Oxid. by KMnO, to phthalic ac.—Ignition w. Zn dust gives 
chrysene. 

} Euxanthone, C,,H,O,.—Pale-yellow (YT1) Ift. or ndl.; sbl. w. dee.—I. aq.; 
e. s. h. alc.; d.s. eth.; s. NaOH or conc. NH,OH w. yellow color.—Green 
color w. FeCl,—PbAc, gives ppt. w. alc. sol—Gives no oxime or phenyl- 
hydrazone. 

+ Brazilin. — Cf. Gen. IV, A!— Cryst. red-brown after exposure to air and 
light. Sol. in NaOH intense red! Taste sweet! 

{+ Daphnetin, C,H,O,.(OH),.—When strongly heated on a watch-glass has a faint 
coumarin-like odor.—Pale yellowish ndl. fr. dil. ale. (preparation fr. 
Schuchardt YT3); s. h. aq.; v. d. s. eth.—FeCl, added to a 1:4000 aq. sol. 
gives a permanent green (G) color, changing to red (RS2) when Na,CO, is 
added (cf. Test 401) —Reduces ammon. AgNO; or Fehling’s sol. instantly — 
Gives a yellow gelatinous ppt. w. PbAc,. 

} Purpurin, 1, 2, 4-Trioxyanthraquinone, C,H,.(CO),.C,H.(OH),.—Deep-red ndl. 
fr. abs. ale.-—Long orange ndl. (+H,O) fr. dil. ale.-—S. aq. w. deep-yellow 
color (no absorption bands).—Sol. in eth. shows absorption bands at E and 
F.—Sol. in NaOH or Na,CO, is bright red w. two absorption bands in the 
green.—Sol. in cone. H,SO, is cherry-red.—Oxid. by HNO, (cf. Test 905-3) 
gives phthalic ac.—W. alumina mordant dyes scarlet. 

Acenaphthenequinone, C,,H,O,.—Sbl. in yellow ndl.—V. d. s. ale. or ec. Ac.— 
Dissolved to an acid by boiling w. KOH.—Reduction w. Zn dust in boiling 
Ac sol. gives acenaphthenon. 

Xanthopurpurin, C,H,.(CO),.C,H,.(OH),.— Yellow ndl. fr. Ac.—Sbl. in orange 
ndl.—S. in Ba(OH), sol. (dif. fr. alizarin and anthrachryson).—S. in NaOH 
is red.—Boiled w. KOH in air gives purpurin (cf. spectrum above).—Igni- 
tion w. Zn dust gives anthracene.—Does not color fibre mordanted w. 
alumina. 

Resorcinphenylacetein, C,,H,,0,.—Mic. brown plates, green by reflected light, 
fr. alc.+Ac.; i. eth. or bz.—Dil. sol. in NaOH shows intense-green fluores- 
cence.—Diacetate, silky ndl. fr. Ac., m. p. 150° d. 

Gentianine, C,,H,O,.Me.—Pale-yellow silky ndl., d. s. h. aq., ale., or eth.; e. s. 
alkalies w. golden-yellow color, reprecipitated by CO,. Diacetate (boiling 
w. acetyl chloride), hair-like ndl. fr. alc., m. p. 196°.—Reduces Tollen’s 
reagent. 











Melting-point 
‘CCA 


————=> 


275 
(284 - 5c.) 


275 


276 


280 


282d. 


283 


289-90 


SUBORDER II, DIV. A, SECT. 1. 211 


(ORDER I.) 





emcees 


COLORED COMPOUNDS.—Solid Species of Determined Melting-point. 


7 Anthraquinone, C,H,.CO.C,H,.CO.—B. p. 380° ¢.—Sbl. in pale-yellow ndl.— 


S. 44 pt. h. ale.; v. d.s. c. ale. or eth—_V. stable, not attacked by boiling 
NaOH or oxid. agents.—Ignition w. Zn dust gives anthracene.—Identify by 
Test 1011! 

1, 3-Dioxyflavone, C,,H,,0,.—Thin pale-yellow tbl.—Sbl. in ndl.—Alm. i. aq.; 
s. h. Ac.; e. s. alkalies w. intense-yellow color.—Ale. sol. is dirty violet w. 
FeCl,.—Split by boiling KOH to acetophenone, phloroglucin, etc. 

2, 3-a-Dioxynaphthoquinone, (HO),.C,,H,.O,.—Orange-red Ift., green by re- 
flected light !—Sbl. in ndl. w. metallic lustre—D. s. h. aq.; v.d_s. ale. or 


eth.—Sol. in NaOH is corn-flower blue; in Na,CO, violet-blue.—E. oxid. to 
phthalic ac. by Test 905-3. 


1, 5-Dioxyanthraquinone (Anthrarufin), C,,H,O..(0H),.—Sbl. in light-yellow 
TooLued lft., alm 1. -ad.s d. 6, aic.- sa eth, aims, NH.OH? Na.CO,,, or 
Ba(OH),; e. s. KOH w. violet-red color.—sS. conc. H,SO, w. very intense- 
red color and fluorescence, distinct even at dilution of 1: 10,000,000 !—Con- 
tinued fusion w. KOH gives salicylic ac., etec.—Ba salt is carmine-red. 


Pyrenequinone, C,,H,O,.—Sbl. w. slight dec. in light purple-red ndl., v. d. s. 
alc., eth., or CS,; s. NaHSO,; s. conc. H,SO, w. brown color.—Ale. sol. +1 
drop NaOH is dark wine-red, unchanged upon shaking w. air.—Ignition w. 
Zn dust in H gives pyrene. 


G-Anthraquinonecarbonic Ac., C,H,:(CO),:C,H;.CO,H.—Yellowish pr. fr. alc., 


v. d. s. alc. or eth.—Sbl.— Boiled w. Zn dust and KOH gives intense-red 
color. 


+ Alizarin, C;H,.(CO),..(CsH».(OH):.—B. p. 430°.—T.t. partly immersed in oil- 
bath at 200° sbl. slowly in OR and O. ndl.—I. aq., v. d. s., alc. or eth. 
—S. in v. dil. NaOH; sol. has red-violet (RV) color. More conce.: sols. 
intensify the color, but the hue remains the same.—NaOH sol. is ppt’d 
by CO, (dif. fr. isopurpurin), Alkaline sol. is ppt’d by BaCl,; not soluble 
in Ba(OH),.—Sol. in conc. H,SO, is purple-red.—Ignition w. Zn dust gives 
anthracene. 

1, 7 (m-)Benzdioxyanthraquinone, C,,H,O,.—Sbl. w. dec. in yellow ndL., s. eth. 
or ale.; s. NaOH w. deep-yellow color. 

Diacenaphthylidendione, C,,H,,0,.—Sbl. brownish-red ndl., v. d. s. bz.—Adds 
Br, (comp. i. alc., lft. fr. CHCl, and lIgr.) m. p. 237°.— Phenylhydrazone, 
brown-red cryst. powder, m. p. 105°-10°. 

2-(m)-Oxyanthraquinone, C,H,.(CO),.C,H;.OH.— Yellow lft. or ndl. fr. ale.—Sbl. 
—Alm. i. aq.; e. s. alc. or eth.; e. s. ammonia giving red-yellow sol.; s. 
Ba(OH), sol., and K salt s. alc. (dif. fr. alizarin).—Ignition w. Zn dust gives 
anthracene (Test 912). 

Alizarin-(-carbonic Ac., (HO),.C,H,:C,0,:C,H,.CO,H.—SbIl. in red ndl., s. ale.— 
The sol. in alkalies is blue. 

Naphthalfluorescein, C,,H,,O;. — Large yellow rhombic pr. fr. eth.—Sol. in dil. 
NaOH is reddish yellow w. green fluorescence.—Acetyl derivative (fr. acetic 
enya... ps 191% 

Anthragallol, C,,H,0,.(OH);—Sbl. at 290° in orange-red ndl.—Brown sol. in 
alc. or eth. —S. alkalies w. green color. — Spectrum, cf. B. 19, 2331. — Igni- 
tion w. Zn dust gives anthracene.—Pb salt, violet-brown ppt. fr. alc. w. 
PbAc,. 

2, 3-Anthraquinonedicarbonic Ac., C, ,H,0,.—Yellow ndl., e. s. ale.—Salts red- 
dish, alm. i. ag.—Warmed w. Zn dust and NH,OH is easily reduced to an- 
thracenedicarbonic ac. 


SSS 


COMPOUNDS CONTAINING ©, H, AND O [ORDER [I]. 
SUBORDER IJ, COLORED COMPOUNDS. 


DIVISION A, (SUPPLEMENTARY) SECTION 2—SOLID SPECIES, 
MOSTLY OF HIGH OR ILL-DEFINED MELTING-POINT, GIVING 
INTENSELY COLORED SOLUTIONS IN DILUTE ALKALI 


[The arrangement of species in this section of the tables is such, that compounds follow one 
another in the order that the hues obtained by dissolving them in dilute caustic soda occupy in 
the spectrum or color standard, beginning with red, and proceeding through orange, yellow, 
green, blue, and violet.—Since the hue as well as the intensity of these colors devends very much 
on the concentration, the colors should be produced and observed under the conditions pre- 
scribed on page 204. The exact order of succession is reasonably well established only for those 
compounds whose color reactions have actually been examined by the author with the aid of 
the color standard. The colors thus determined are distinguished from those based on the 
verbal description of other authorities by being followed by a color symbol (e.g., red=R). The 
preparations used in most of the writer’s experiments on the species of this supplementary sec- 
tion were commercial products—sometimes pastes—from reliable manufacturers. The best 
preparations of this class are, of course, liable to slight differences in composition, and are never 
absolutely homogeneous. ] 





COLORED COMPOUNDS.—Solid Species, giving intensely 


Color of Solution in very ) , ‘ L 
colored solutions in dilute Alkali. 


dilute NaOH. 


R-RV. Hematoxylin, C,,H,,O,+3H,0.—Brown cryst. (colorless when 
Intense VB in conc. NaOH. pure).—Taste sweet.—Sol. in conc. NaOH, deep violet (V 
or BV), becoming (R) on acidification w. HCl.—Sol in conc. 

H,SO, orange (O).—Cf. Sec. 1, m. p. 140°. 





Red (R). Brazilin.—Red-brown cryst (colorless when pure).—Taste 
sweet.—Cf. Gen. IV, A,m. p. abt. 250°. 
Red (R) Flavopurpurin, C,,H,0,.(0H),.—Yellow ndl. or YOS1 paste.— 


(slightly RV). 
“Deep red.” 


‘“Vine red.” 


Red (R). 


Fuchsine red. 


Intense red to brown 


(yellow-green fluorescence). 


Red (w. green-yellow 
fluorescence). 


Red. 


Carmine-red. 


D. s. h. aq.; e. s. h. ale.-—Sol. in conc. H,SO, is red. 

2, 7-Dioxyanthraquinone, C,,H,O,.(O0H),+H,0O, [Isoanthraflavic. 
Ac.].—Yellow cryst.; m. p. a. 330° after losing cryst. aq. at 
150°.—Sbl.—Sol. in conc. H,SO,, deep red.—s. ce. Ba(OH),. 
sol ; s. alc.; alm. 1. eth. 

Trioxyaurine, C,,H,O.(OH),.—Dark-red lft. fr. eth.-ale. 

Purpurin, C,H,.(CO),.C,H.(OH),._{Cf. Sec. 1, m. p. 256°.}— 
Orange-red (ORS1) paste or ndl.—Sol.in cone. H,50,, R-OR, 
changing to YO on dilution w. aq. 

Cresolaurine, C,.H,,O.(OH),.—Amorph. red powder; i. aq.; d. 
s. eth.—Sol. in Ac, yellow. 

Resorcinoxalein, C,,H,O,.(OH),;.—Red powder.—S. in cone, 
H.SO, w. emerald-green color.—The alkaline sol. diluted to 
a pale-yellow shows moss-green fluorescence, 

Beep C,.H,,0,(OH),. — Red-brown grains, v. d. s. 
alc. 

Carminic Ac., C,,H,,0,).—Red pr. fr. alc., or red-brown powder. 
E. s. aq.; sol. yellowish red.—Aq. sol. gives purple ppt. w. 
baryta sol.—Alc. sol. heated w. aniline gives ruby-red cryst.. 
anilide, m. p. 190° d. 

Brazilein, C,,H,,0;.—Cryst. w. 1H,O. Powder reddish-brown. 
D. s. aq.; sol. rose-red w. orange fluorescence.—Alkaline sol. 
browns in air.—Triacetyl deriv., yellow lft. fr. ale., m. p. 
203°-7°. 





212 


SUBORDER II, DIV. A, (SUPPLEMENTARY) SECT, 2. 213 


Color of Solution in very 
dilute NaOH. 


Brownish red 
(fluorescent). 


Orange-red (OR) 
(not fluorescent). 


Yellow-red (not 
fluorescent). 


Orange. 


Red to yellow 


(according to dilution). 


Intense yellow-green 
(YG) fluorescence. 


Yellow-orange (YO). 


Yellowish brown. 


Yellowish brown. 


Orange-yellow. 


Orange-yellow (OY). 


Orange-yellow. 


Yellow. 


Deep yellow. 


Green. 


(ORDER I.) 


COLORED COMPOUNDS.—Solid Species, giving intensely 
colored solutions in dilute Alkali. 


Fisetin, C,,H,,0,+4H,O.—Cryst. in lemon-yellow ndl. w. 4 aq. 


(lost at 110°). M. p. a. 360° d.—S. ale. ; alm. i. aq.—PbAc, 
gives orange-yellow ppt. in alc. sol.— Reduces Fehling’s sol. 
hot.—Tetraacetate, ndl. fr. ale., m. p. 200°-1°. 

Auvine, C,,H,.0.(OH), and Rosolic Ac., Me.C,,H,,0.(OH),.— 
Commercial article a mixture w. very variable m. p (some- 
times as low as 90° or 100°), and w. strong odor of phenol.— 
Color of powder RO. Lumps show conchoidal fracture and 
greenish metallic reflections.—Sol. in cone. H,SO, yellow 
(OY-Y).—A (1:5000) sol. in very dil. NaOH shows absorp- 
tion band at D4E to b. More conc. sol. shows one-sided 
absorption fr, violet to D line.—Sol. in alc. orange (QO). 


Resaurine, C,,H,,O.(OH),.—Amorph. light brick-red powder; 
é. 8. alc.; alm. i. eth. 

2, 6-Dioxyanthraquinone (Anthraflavic Ac.), C,,H,O.(OH),.— 
Sbl. in yellow Ift., m. p. a. 330°.—Sol. in conc. H,SO, yellow, 
showing broad absorption band between blue and green.— 
DSC nalecnl seri. 

Fluorescein, C.,.H,,0,.(0H),.—Yellow-orange (YOS1) powder. 
—Sol. in conc. H,SO, (Y) w. slight greenish fluorescence. — 
I. c. aq.; d.s. alc. or eth.—Paper stained a pale yellow by 
dil. sol. in Ac becomes pink when held in steam from boiling 
Br water.—The very dil. sol. in dil. NaOH shows a distinct 
absorption band from a little to right of EK to just beyond F. 


Phenacetolin (Phenacetein), C,,H,,0O,.—Chocolate or red-brown 
powder. M. p. a. 330°. Sol. in conc H,SO, (YOS1-2) — 
I. aq.; sol. in alc. orange; in dil. HCl yellow; in dil. am- 
monia violet-red (VR). (Colors as given by a sample pur- 
chased from Merck.) 

Resorcinbenzeine, C,,H,.0.(OH),.—Pr. or Ift., violet- or brown- 
ish-red; yellow by transmitted light. E s_ h. ale. when 
freshly precipitated, otherwise v. d. s.—Loses aq. at 130°.— 
Dil. ammon., sol. red-violet and fluorescent. 

Galloflavin, C,,H,O,(?).—Greenish-yellow lft. Sol. in cone. 
H,SO, orange.—D. s. h. alc.; sol. clear yellow w. faint-green 
fluorescence. 

Alizarin Yellow “ C,”” CH,.CO.C,H,(OH),.— Yellowish paste, e. s. 
h. aq.—Sol. in conc. H,SO, yellowish.—Cf. Gallacetophenone 
(lV, Aymp. 168°) 

Alizarin Yellow ‘‘A,” Ph.CO.C.H,.(OH);.—Paste, gray yellow 
(light YA). EH. s. h. aq.—sSol. in conc. H,SO, clear yellow 
(Y). 

Quercetin, C,,H,,0O,+7H,0.—Lemon-yellow cryst. powder. 
Loses H,O at 130°.—S. 280 pt. h aq. or 229 pt. c. ale.—M. 
p. a. 250° (r. h.).—Ale. sol. dark green w. FeCl,, turning 
dark red on warming; gives brick-red ppt. w. PbAc,. 

Croconic Ac., CO:C:C:(CO,H),+3H,0.—Pale sulphur-yellow 
ndl. or grains, e. s. aq.; s. ale.-—Sbl. after losing aq. at 100°. 
—DaCl, gives lemon-yellow ppt. of BaA+14H,O0.—Ag salt, 
orange-red ppt. 

Luteolin, C,,H,,0,-+2H,0(?).—Yellow ndl., m. p. a. 320° d— 
Sbl.—S. 14,000 pt. ¢. aq., 37 pt. ale., or 625 pt eth.—Taste, 
bitter-astringent.—Sol. green w. little FeCl,, brown-red w. 
larger quantity.—Sol. in conc. H,SO, yellowish green giving 
violet ppt. on dilution.—CaCl, gives orange ppt., which 
becomes red and cryst. on boiling. 

a-Naphtholbenzeine, C;,H,,(O0H),.0.—Brown powder, i aq.; s. 
ale., eth., or bz. w. yellow-red color.—The green sol. in alka- 
lies is turned reddish yellow by acids. 





SUBORDER II, DIV. A, (SUPPLEMENTARY) SECT. 2. 


(ORDER I.) 





Color of Solution in very 
dilute NaOH. 


Intense G-YG. 


Blue. 


Cornflower-blue. 


Cornflower-blue. 


Intense blue. 


Intense blue (B). 


Intense Blue to VRT2 


(according to concentration). 


Impure Violet. 
Blue (B) w. conc. NaOH. 


Blue-violet. 


Red-violet (RV). 


Violet-red. 


Violet-red. 
Violet-red (VR). 


RV 
(Intense VB-V w. conc. 
NaOH). 





COLORED COMPOUNDS.—Solid Species, giving intensely 
colored solutions in dilute Alkali. 





Coeruleine, C,,H,O,.— Black powd. or paste, i. aq. or ale.—Sol. 
in cone. H,SO, ‘‘dirty yellow-brown” (broken OY much 
darker than dark OY <A). 

Alizarincyanin ‘‘R,’’ C,,H,0,.(0H),.—Brown lft. or paste.— 

Dist. undec.—Sol. in conc. H,SO, blue w. red fluorescence. 

2, 3-Dioxyanthraquinone, C,,H,(OH),.0,.—Orange-yel. ndl. fr. 
Ac, v. d. s. h. ale. or eth.—Sol. in cone. H,SO, blood-red.— 
Ba salt dark-blue ppt. 

5, 6-6-Dioxynaphthoquinone(1, 4),(Naphthazarin), C,,H,O,.(OH),. 
—Sbl. in red-brown ndl.—Sol. in cone. H,SO, fuchsine red. 
—D.s. h. alc.; cryst. fr. alc. sol. in ‘‘green-brown” ndl.— 
Diacetate, yellow ndl., m. p. 192°. 

Pyrogalloquinone, C,,H,,0).—Sbl. in garnet-red ndl. M. p. a. 
220°.—D. s. alc.; s. eth.—Sol. in conc. H,SO, carmine-red 
or on addition of trace of nitrous acid, intense violet. Br 
in Ac sol. gives clear red tetrabrom-derivative, m. p. 202°—-4°. 


Alkannin, C,,H,,O,.—Dark red-brown resinous mass (softens 
below 100°).—I. aq.—Sol. in ale. orange-red (OR), and when 
dilute shows conspicuous absorption bands, one at Eb, the 
other at DE; also two easily overlooked bands, one at F, 
and the other at DiC. The sol. in ammonia is blue with 
conspicuous absorption bands D and D3C. 


Galleine, C,,H,,0;—Dark red-brown powder, or small cryst. w. 
green metallic reflections (also described as violet paste or 
powder). S. w. red-brown color in warm alc.—Heated w. 
juming H,SO, gives olive-yellow sol. (containing cceruleine) 
from which olive flocks separate on dilution w. aq.; the ppt. 
dissolves w. intense green color (G—YG) in dil. NaOH. 

Rufigallic Ac., C,,H,O,.(0H),.—Orange-red (ORS2) cryst. or 
brown-red powder, i. aq.—Sol. in cone H,SO, intense red, 
becoming yellow on dilution. 

Alizarin Bordeaux, C,,H,O,.(OH),.—Sbl. in deep-red ndl. (green 
w. metallic lustre by reflected light)—Not melted at 275°. 
—Sol. inc. conc. H,SO, has intense blue-violet color—Baryta 
water gives blue ppt. w. alc. sol.—Tetra acetyl deriv , m. p. 
201°. . 

Alizarin, C,,H,O,.(O0H),.—(Cf. Sec. 1, m. p. 289°-90°.)—Sbl. in 
orange (O) ndl.—(‘‘ Paste’? OYS1-YOS1).—Sol. in cone. 
H,SO, is red (R); dilution w. aq. gives OY ppt. 

Benzaurine, C,,H,,(OH);.—Brick-red powder, e s. alc. or eth.; 
i. aq.—Color of alkaline solution changed to yellow by acids, 

Resorcincinnamyleine, C,,H,,0.(OH),+H,O.—Brown amorph. 
powder; at 100° becomes green w. metallic lustre —Alc. 
sol. red. 

Iso or Anthrapurpurin, C,,H,O,.(0H),.—Orange ndl. fr. alc., 
m. p. a. 330°.—(Paste YOS1). E.s. ale.; d.s. h. aq. or eth. 
——Sol. in cone. H,SO, red, giving OY ppt. on dilution w. aq. 

Hemateine, C,,H,.0,.—Thin, mic., gray-green, water-free cryst. 
w. yellowish-green metallic lustre; commercial product a 
dark-brown powder. D.s. aq. or alc.; v. d.s. eth.—Sol. in 
conc. NaOH deep violet or blue-violet (V or BV), becoming 
red (R) on acidification w. HCl. Sol. in conc. H,SO, orange 
(O).—Cryst. darken and decompose abt. 250° (dif. fr. 
heematoxylin). 





Boiling-point Specific 
(C2): Gravity. 
87-5-8 0-973(22°) 
108 0-948(19) 
115-16 
128 0-934(1°/,) 
138 0-908 (??/,) 
163 0-881(1°/,) 
175-6 1e072(4*/,) 


216-18: 


COMPOUNDS CONTAINING C, H, AND O [ORDER I]. 
SUBORDER I, COLORED COMPOUNDS. 


DIVISION B,—LIQUID SPECIES. 


1-104(14/,) 








COLORED COMPOUNDS.—Liquid Species. 





+ Diacetyl, Me.CO.CO.Me.— Yellow (Y) liquid of peculiar sweet- 
ish-pungent odor! Vapor w. color of Cl.—S. 4 pt. aq. at 15°. 
—Treatment w. alkali by Test IV, 2 gives an opaque brown 
sol. !—} To identify: Mix in a 3-inch test-tube 1 drop of the 
ketone, 1 ce. of aq., and 0-5 grm. of hydroxylamine hydro- 
chloride. Boil. A heavy eryst. ppt. of the pure white 
dioxime separates at once. Cool. Collect on a small filter. 
Wash w. c. aq. Dry at 100° for 15 min. The diacetyl- 
dioxime formed melts at 234-5° (uncor.) ! 

Acetylpropionyl, Me.CO.CO.Et.—Color, odor, and behavior 
towards alkali as w. diacetyl above.—S. in 15 pt. ce. aq.— 
M. p. of dioxime 170°-2°! 

Acetylisobutyryl, Me.CO.CO.CH.Me,.—Color, odor, and _ be- 
havior towards alkali as w. diacetyl above; but d. s. aq. 
Acetylbutyryl, Me.CO.CO.Pr.—Color, odor, and behavior to- 
wards alkali as w. diacetyl above.—M. p. of dioxime 168°! 
Acetylisovaleryl, Me.CO.CO. Bu.—Properties as for preceding 

comp.—M. p. of dioxime 171°-2°! 

Acetylisocaproyl, Me.CO.CO.(CH,),.CH.Me,.—Properties as for 
preceding comp —M. p. of dioxime 172°-3°! 

Phenyldiacetyl, Me.CO.CO.CH,.Ph.—Viscous yellow oil. Odor 
honey-like, but pungent 

+t Acetylbenzoyl, Me.CO.CO.Ph.—Yellow oil of peculiar sweet- 


ish-pungent odor. Vapors yellow. Browns w. NaOH in 
Test IV, 2—M. p. of dioxime 239°-40° (cf. B. 22, 2129). 





215 


NUMBERED SPECIFIC TESTS FOR SPECIES OF 
SUBORDER II. 
[TESTS 1011-1100] 


torr. Anthracuinone. (Properties tabulated on p. 211.) 


Boil together in a test-tube for half a minute, a mixture of 5 cc. of an aqueous sodium- 
hydroxide solution (1:20), 0.01 grm. of the finely powdered quinone, and 0.2 grm. of 
zine dust. Filter quickly while hot through a plaited filter. Anthraquinone gives a deep- 
red (about OR) colored filtrate, which quickly becomes decolorized on shaking in contact 
with the air, in consequence of absorption of oxygen; while a flocculent precipitate of light- 
.colored anthraquinone separates. Upon adding more zinc dust, heating, filtering, and 
shaking, the phenomena described may be repeatedly reproduced. 

This color reaction, which in the modified form as described by Claus (B. 10,926), 
is still more delicate and striking, although less convenient, is, in connection with its physical 
properties, the only test that will usually be needed for the identification of anthraquinone. 


1012. Benzoquinone. (Properties tabulated on p. 206.) 


Dissolve 0.05 grm. of the substance in 5 ce. of hot alcohol. Add 10 drops of aniline. 
Boil one minute. Cool. Filter. Wash the precipitate with 3 cc. of hot alcohol. Transfer 
to a test-tube, and boil with 20 cc. of glacial acetic acid. Cool. Filter. Dry, and observe 
the behavior of the compound on heating in a melting-point capillary. 

2, §-Dianilinoquinone, the product in this test, is obtained in the form of very insoluble 
and lustrous scales of a peculiar violet-red color, which, when dry, give a brownish “streak.” 
It sublimes without melting at 325°-330° (uncor.). 


1013-a-Naphthoquinone. (Properties tabulated on p. 207.) 


Boil together for one minute in a test-tube 0.05 grm. of the quinone, 5 drops of aniline, 
and 2 ce. of alcohol. Cool. Add 10 ce. of water and 1 ce. of acetic acid, and shake. Filter 
off the precipitate, and wash with cold water. Recrystallize from 10 ce. of boiling dilute 
alcohol (1:1). (Very vigorous shaking is sometimes necessary to start the separation of 
crystals from the well-cooled solution.) Wash with 3 cc. of the dilute alcohol. Press on a 
porous tile. Dry 15 minutes at 100°, and determine the melting-point. 

2-Anilinonaphthoquinone, the product in this test, is obtained as a fluffy dark-red 
(R-RS1) powder consisting of micro-crystalline needles, and melts at 190° (uncor.). 


1014. Phenanthrenequinone. (Properties tabulated on p. 209.) 


1. (Color reaction.)—Apply the reaction with caustic and zine dust described in Test 
1011. The color produced by phenarthrene is a quite pure and intense green. It is seen 
to the best advantage on the edges of the plaited filter. The green filtrate when vigorously 
shaken absorbs oxygen from the air (less rapidly than in the test for anthraquinone), and 
becomes yellowish. 

2. Dissolve 0.05 grm. of the quinone in a mixture of 2 ec. of fuming nitric acid (sp. gr. 
1.48) and 2 ce. of sulphuric acid (sp. gr. 1.84). Boil gently for one minute. Cool, and 
pour into 10 cc. of cold water. Collect on a filter, and wash thoroughly with hot water. 
Dissolve the washed precipitate in 15 ce. of boiling glacial acetic acid. Cool, and filter. 
Wash the precipitate with 3 cc. of glacial acetic acid. Dry 15 minutes at 125°, and deter- 
mine the melting-point. 

The product in this test a-2, 7-Dinitrophenanthrenequinone is a yellowish crystal- 
line precipitate which begins to turn brown about 270° (uncor.), decomposes to a sticky 
mass at 285° (uncor.), and completely liquefies to a black drop at 294° (uncor.). a 


CHAPTER XIIL 
SPECIAL METHODS, APPARATUS, AND REAGENTS. 


Kvery department of experimental science gradually acquires a more or less 
considerable body of special laboratory methods which experience has proved 
are best adapted to meet its peculiar requirements. These constitute its special 
technique. ‘The purpose of the present chapter is to bring together for explana- 
tion or comment a few methods of this kind which will be helpful to persons using 
the procedures of this volume. It is assumed that the reader is already familiar 
with the simpler manipulations of analytical and organic chemistry, and of experi- 
mental physics. 


MELTING- AND BOILING-POINTS. 


The numerical values of the melting- and boiling-points of organic compounds 
have such a wide range, and can be approximately determined with so little diffi- 
culty, that they are more regularly met with in the original descriptions of new 
species than any other physical constants. Unfortunately, however, only a very 
small fraction of these values are the result of fully corrected thermometric meas- 
urements, or of observations made under conditions that can be exactly duplicated. 

In using published data of this kind we have no choice but to assume that all 
necessary corrections for irregularities in the bore of the thermometer capillary, 
the value of its scale unit, and the position of its zero-point at different times 
have been made, though it is to be feared that chemists are often very negligent 
in this particular. But a very serious uncertainty always exists as to the proper 
interpretation to put upon values obtained at higher temperatures that are not 
followed by the word “corrected” or ‘‘uncorrected.” In the neighborhood of 
300°, a melting-point that has been corrected for stem-exposure is very likely to 
be about 10° higher than if uncorrected—a difference which is several times greater 
than the probable combined error from all other causes. What proportion of 
‘the great body of these unclassified melting- and boiling-points in chemical litera- 
ture has been corrected for stem-exposure can only be surmised; but the author’s 
experience inclines him to accept the conclusion of Meyer and Jacobson’s ‘‘ Lehr- 
buch der organischen Chemie” (Vol. I, pp. 115, 116), that among organic chemists 
the unqualified ‘melting-point’’ has come generally to mean one uncorrected for 
stem-exposure; while the unqualified “ boiling-point”’ (boiling-points often being 
taken in long-necked distilling flasks or with short-stemmed thermometers) is 
in most cases substantially ‘“corrected.”” The confusion arising from this unfor- 
tunate and unscientific practice can only be entirely remedied by the careful 
redetermination of all the unqualified data. 

The melting-points given in the “ numbered specific tests” of this volume are all 
uncorrected for stem-exposure; but they may be readily converted into “corrected” 
melting-points by simply adding the proper correction from the following empir- 


ical table. This table is applicable only to observations made in an apparatus of 
217 


218 SPECIAL METHODS, APPARATUS, AND REAGENTS. 


approximately the form and dimensions shown in Fig. 5, and the larger corrections 

may even then leave a residual error of about half a degree. 

[Table of stem-exposure corrections to be added to the direct readings of an otherwise corrected 
360° rod thermometer, with a diameter of 5 mm., and a degree length of 0.85 mm., when 
immersed in a liquid bath from the —10° point, and with 100° of the stem within the air- 
space of the inner tube of an apparatus of the form and dimensions described below.] 














Observation Correction Observation Correction Observation Correction 
COLON: (sy (CS): (C2). (C2) (G2): 
50 0.1 140 2.0 230 Giz 
60 0.2 150 2.3 240 fae 
70 0.3 160 2a 250 7.8 
80 0.5 170 3.1 260 8.4 
90 Ox 180 3.6 270 9.0 
100 0.9 190 AS}. 280 9.6 
110 Lee 200 4.6 290 10.2 
120 1.4 210 5.3 300 10.9 
130 shay 220 6.0 





The Usual Method for Determining Melting-points.—These determinations 
are most conveniently made in the apparatus figured, because the closed flask 
prevents the free escape of fumes into the laboratory when high temperatures 
are being used, and also excludes dust and moisture from the bath to such an 
extent that frequent renewal of the liquid is unnecessary. In a laboratory 
where melting-points are frequently taken, it is 
well to have two such flasks, one for high and the 
other for low temperature determinations, always 
in readiness for immediate use. 

The flasks should be round-bottomed, with 
bulbs 65 mm. in diameter, and with necks 75 mm. 
in length and 20 mm. in diameter. Their capacity is 
about 200 cc. The inner tube, A, is a test-tube 
with a diameter of 15 mm., which hangs freely 
suspended by its flanged lip. Both the inner tube 
and the flask are filled with a clear liquid to the 
level B, it being a very bad practice to use the 
test-tube as an air-bath. 

The best bath for temperatures between 0° and 
220° is probably colorless sulphuric acid of 1.84 
specific gravity. The acid in the inner tube is, it is 
true, easily browned by contact with organic matter 
of any kind, and so must be renewed occasionally; 
but it has the advantage over dissolved or molten 
solids that when splashed upon the cool upper 
parts of the tube it drains back quickly without 
leaving any cloudy film to interfere with a clear view 
of the lower part of the thermometer scale. 

A bath highly to be recommended for tem- 
peratures between 220° and 320°, in connection 
with the foregoing,—and which may be used, though less advantageously, for the 


































































































Fia. 5. 


SPECIAL METHODS, APPARATUS, AND REAGENTS. 219 


entire range of temperature between 15° and 320°,—is prepared by cautiously 
heating in a porcelain casserole under a hood until boiling ceases at the higher 
temperature, a mixture of 70 parts by weight of concentrated sulphuric acid and 
30 parts of neutral potassium sulphate, and stirring constantly until the sulphate 
is completely dissolved; or by similar treatment of a mixture of 55 parts by weight 
of the acid with 45 parts of acid potassium sulphate. The mixture has the con- 
sistency of glycerine,* and does not fume so badly as to prevent the use of rubber 
bands for attaching melting-point capillaries to the thermometer. It is less cor- 
rosive and less easily discolored by traces of organic matter than sulphuric acid. 

The phenomenon of fusion is observed in a thin-walled glass capillary, sealed 
at the lower end J, which is occupied by a few milligrams of the substance. These 
melting-point tubes should have a length of 6 to 7 cm. and an internal diameter 
of 1 mm. They are most readily made from rather soft glass tubes having an 
internal diameter not less than 1 cm.—not, as is often done, from small-bore 
tubing. A piece of such tubing, of convenient length, is supported at both 
ends and rotated in a blast-lamp flame until a ring 2 cm. long has been heated to 
dull redness. Then, upon separating the hands rather slowly, until both arms 
are outstretched at full length horizontally from the shoulders, a capillary of the 
desired diamete~, and nearly two meters in length, may be drawn out in a single 
operation. 

To charge the melting-point capillary, force its open end downward into a 
small mound of the finely powdered substance. Then, holding upward the open 
end, which will now be closed by a short plug of the compacted powder, draw the 
flat side of a file horizontally across the tube a little below the substance. The 
powder, loosened by the vibrations set up in the glass, will quickly slide down into 
the desired position. The charged capillary is now attached to the thermometer 
by a narrow rubber band sliced off from a piece of rubber tubing. The band should 
be placed 2 cm. above the surface of the bath, and the substance in the capillary 
should be situated opposite the middle of the thermometer-bulb. If a sulphuric 
acid bath should be used at temperatures above 170°, a piece of fine platinum 
wire, which will not be attacked by the hot acid fumes, should be wound spirally 
around tube and thermometer, as a substitute for the band. With the potassium 

* After long exposure to the air it may become semi-solid through absorption of water, 
but is easily liquefied again by heat. When a melting-point above 300° is to be taken with a 
bath that has not been heated much above 250° for some weeks, it is advisable first to boil it 
for a few minutes. Otherwise the bubbles of steam given off in the neighborhood of 300° will 
cause bumping and interfere with the observation. Under certain obscure conditions the 
mixture may solidify to a hard mass, with a considerable rise of temperature. But this is a rare 
occurrence, and when it happens a short boiling will bring the bath back to its normal state. 

By increasing the proportion of neutral sulphate from 30% to 40% this bath may be used 
for temperatures up to 370°. Such a bath remains pasty until the temperature has fallen to 


90°-60°. Either of these sulphate baths if slightly darkened by organic matter may be cleared 
by a short heating above 300° ; 

As a bath for temperatures between 370° and 500° fused zine chloride, free from dust, may 
be employed. Since it is very apt to crack any flask in which it may be allowed to solidify on 
cooling, it should be poured out upon a clean tile as soon as the temperature has fallen to about 
280°. ; ; 

+ The melting-points of a few compounds which fuse at high temperatures with decompo- 
sition and loss of water, carbon dioxide, or ammonia, have been found to be sharper when 
observed in capillaries sealed at both ends. These melting-points are, however, of very little 
value unless accompanied by a statement of all the dimensions of the capillary, and of the 
quantity of substance fused; for they will be found often to vary many degrees with a change 
in these conditions, because of differences in the gas pressures of the decomposition products. 


220 SPECIAL METHODS, APPARATUS, AND REAGENTS. 


sulphate bath, however, rubber bands are not seriously attacked, even when the 
bath is at 300°. 

For general convenience in manipulation, and because it is probable that a 
majority of the organic melting-points on record have been obtained by instru- 
ments of approximately these dimensions, the use of a thermometer with a grad- 
uation extending from —25° to + 360°, with degree-marks about 0.85 mm. apart, 
is to be preferred. A thin stem (diameter about 5 mm.) is advantageous, as it 
Saves space and acquires the temperature of the bath quickly. The direct read- 
ings of such a thermometer may be sufficiently corrected for stem-exposure by 
means of the table on page 218. (For a discussion of the other thermometric 
corrections cf. Crafts, Am. V, 309.) 

The proper rate for heating in a melting-point determination depends some- 
what on the behavior of the compound. Substances that melt without any decom- 
position are always to be heated very slowly, as the melting-point is approached. 
An average rise of 2° per minute for the last 5° is fast enough; for it is only by 
proceeding slowly that we can feel reasonably sure that the substance and ther- 
mometer are both at the same temperature. On the other hand, with substances 
that begin to decompose slightly before fusion, slow heating increases the quantity 
of decomposition products, and gives mixtures which will begin to melt much 
too low. Substances of this class should be heated rapidly to within a few degrees 
of their probable melting-point, and then at a rate of about 5° per minute. 

As has been shown by Reissert* and others, the true melting-point of com- 
pounds that melt without decomposition, when the fusion is observed in capillary 
tubes, lies much nearer to the temperature observed at the moment when minute 
droplets are first formed from particles of fine powder in actual contact with the 
capillary wall, than that at which a more considerable portion of the mass has 
become liquid; for, while the temperature of the melting compound must remain 
constant during the period between incipient and complete fusion,—in obedience 
to the well-known law,—that of the bath and thermometer is meanwhile gradually 
rising. The temperature recorded just before the moment of complete liquefac- 
tion will, however, generally be nearer its true melting-point for any compound 
that melts with slight decomposition, or contains traces of impurities. Differences 
of 2° between melting-points obtained by different methods of observation are 
quite possible. 

In taking the melting-points of compounds that fuse to mobile liquids, a very 
common practice among organic chemists—regardless of theoretical considera- 
tions—seems to be to observe the thermometer at the moment when the first 
clear drop of sufficient size to detach itself from the solid mass and roll down the 
capillary under the influence of gravity makes its appearance. As this moment 
is usually easier to fix than that of the appearance of the first minute droplets, 
and with pure stable compounds gives values nearer the true melting-point than 


* A. Reissert, B. 23, 2239. 

The true melting-point of a compound is its temperature of fusion as recorded by a 
thermometer immersed in a considerable quantity of the melting mass, as is described on page 
225. It usually differs somewhat from the melting-point that would be found by using the 
capillary method. The melting-points of the specific descriptions in this volume are all capillary 
melting-points. 


SPECIAL METHODS, APPARATUS, AND REAGENTS. 221 


the moment of complete fusion, or than the moment of incipient fusion with com- 
pounds that are not free from every trace of impurity, this method of observation 
is to be recommended as on the whole the most satisfactory for analytical use. 

The Usual Method for Determining Boiling-points.—The apparatus required 
is shown in Fig. 6. The bulb of the distilling-flask has a capacity of 10 to 15 cc., 
and the volume of liquid to be distilled is 
preferably 5 to 10cc. The bottom of the 
flask rests in a circular opening cut by a 
brass cork-borer in a square piece of asbestos 
board, A, having a thickness of 3 mm. 
The perforation should have a diameter of 
about 2 cm. and be slightly beveled by a 
file on the upper edge, to make it fit closely 
to the surface of the flask. If the contact 
is not good at all points when the flask is 
pressed down into the opening, it may be 
improved by the use of an annular washer 
of thin asbestos paper, B, which will pre- 
vent the upward leakage of hot gases from 
the flame. C is a threefold wrapping of 
asbestos paper reaching to a point 1 cm. 
above the side tube. Its object is to prevent sudden condensation of vapor and 
consequent thermometric fluctuations, if the apparatus should happen to be ex- 
posed to a draft of cold air. The thermometer should be thin-stemmed, and 
inserted along the central axis of the neck of the flask, with its bulb well below 
the side tube. If there is a stem-exposure, a light auxiliary thermometer—not 
shown in the cut—will be attached to the main thermometer by rubber bands 
with its bulb opposite to the middle of the exposed mercury column. The neck 
of the distilling-flask above the side tube should be as short as possible, since, if the 
space which it contains is large, it will not be entirely filled with vapor at the tem- 
perature of the boiling liquid. 

Unless the substance shows marked signs of decomposition when boiled, dis- 
til slowly, i.e., at a uniform rate of about 0.5 cc. per minute. Since some time 
will elapse before the thermometer can acquire the temperature of the vapor, 
little significance shoula be attached to readings taken before the end of the first 
minute after the fall of the first drop of distillate. Interrupt the distillation when 
the liquid remaining in the flask has fallen below the level of the asbestos diaphragm. 
Any reading taken after this point has been reached, when less than 1 cc. will remain 
in the flask, will be influenced by superheating,* and should be rejected. 


























Fria, 6. 


* Superheating.—The great advantage to be derived from the use of asbestos screens in 
this determination is not generally appreciated; and it will surprise many to learn that a boil- 
ing-point taken in a 10-cc. flask with the simple precautions given, will be more worthy of con- 
fidence than one made with a tenfold greater quantity of substance in which they are omitted. 
Much time and material would be saved if such screens were generally utilized in fractional dis- 
tillations whenever the quantity of material to be boiled is rather small. As practical illus- 
trations of the danger of superheating the vapor of liquids boiling in unscreened flasks, the follow- 
ing instances, which are copied from the author’s note-book, will be of interest: 

(1) 5 ce. of ‘‘frozen,’’ thiophene-free benzene was distilled in a 10-cc. distilling-flask of the 
usual pattern; first, rapidly, the flask being unscreened; then, slowly, with the bottom of the 


222 SPECIAL METHODS, APPARATUS, AND REAGENTS. 


In the case of pure compounds that boil without decomposition, the difference 
between the first and last significant readings (after being corrected for stem- 
exposure, if the temperature of the auxiliary thermometer rises considerably during 
the experiment) ought not to amount to one degree. The boiling-points of sub- 
stances that suffer slight decomposition during distillation are often expressed as 
falling between two limits. 

The stem-exposure correction may be found by substitution in the formula 
N(T —t)X0.000154; in which N represents the length of the exposed thread cf 
mercury (expressed in degrees); 7’, the observed boiling-point; t, the temperature of 
the auxiliary; and 0.000154, the apparent coefficient of expansion of mercury in glass. 

To reduce boiling-points taken under pressures between 720 and 780 mm. to 
their approximate values at 760 mm., apply a correction of 0.1° C. for every 2.7 
mm., the correction having a plus sign below 760 mm., and a minus sign with 
higher pressures. 

Determination of Boiling-points of Small Quantities.*—If only a few drops 
of liquid can be spared for a boiling-point determination, the following procedure 
should be used: About three drops of the liquid are introduced into a narrow 
glass tube, A, by means of a medicine-dropper having a long capillary point. The 
tube A should have a length of 6 to 7 cm. and an internal diameter 
of 2.5 to 3 mm. It is sealed at the lower end; attached to the 
thermometer by a rubber band; and is heated in the bath used for 
determining melting-points (page 218, Fig. 5). To prevent the super- 
heating, and violent boiling that would otherwise occur on heating, 
the slender capillary B is dropped into the liquid. These tubes are 
made from narrow pieces of melting-point capillary (cf. page 219), by 
heating the glass at the point Cin the edge of a flame, the tube being 
supported at both ends, until the walls melt and fuse together. This 
leaves a little chamber under C, closed above, but open below, which 
is to be cut off so as to have a length of 3 mm. 

To make the determination, the temperature of the bath is grad- 
ually raised until the single air-bubbles that begin to rise from the capil- 
lary chamber some degrees below the boiling-point are replaced by an 
apparently uninterrupted thread of small vapor-bubbles. The lamp 
should now be removed, until boiling ceases and the liquid is seen to 
be about to recede into the capillary chamber. The temperature at the 
moment of recession is that at which the liquid remaining in the tube would begin to 
boil. In the case of compounds that are not quite pure it is not necessarily 














flask resting in an asbestos diaphragm 12 mm. in diameter. The temperatures observed at 
intervals of one minute in the case of the unscreened flask were—80.3°, 81.0°, 82.2°, 86.0°, and, 
as the last drops disappeared, 93°. With the screened flask the minute observations noted 
were—79.8°, 80.0°, 80.0°, 80.0°, 80.0°, 80.0°, 80.1°, 80.1°, 80.2°, of which the last two readings 
were taken after the liquid had reached the level of the screen, and of which the first was proba- 
bly registered before the thermometer had quite acquired the temperature of the heated vapor. 

(2) 17 cc. of pure water was rapidly distilled from an unscreened 50-cc. flask. The pre- 
caution was taken not to allow the visible flame of the burner to play on the glass above the 
surface of the liquid, and boiling was stopped when 5 cc. of water remained in the flask. The 
readings obtained were 100.2°, 102.0°, 106°, 108.0°, 108.0°. ‘The intervals between all these 
readings, with the exception of that between the last two, which was 30 seconds, were 1 minute, 
as in the experiment with benzene. 

* Siwoloboff’s method (slightly modified), B. 19, 795. 


SPECIAL METHODS, APPARATUS, AND REAGENTS. 223 


identical with that of the chief constituent of the mixture. Hence, after noting 
the temperature at which recession begins, heat should always be applied again 
until the continuous thread of bubbles reappears, and the boiling then continued 
until nearly half the liquid has evaporated from the tube. If the temperature 
of the second recession is identical with the first, it is probably the boiling-point 
of a pure compound. J} zt differs a few degrees from the first, it may be accepted as 
the most probable bowling-porint of the chief constituent of the mixture. 

If the capillary chamber should entirely fill with liquid while the observation 
of the first recession is being made, it will have to be emptied, or the capillary 
replaced by a fresh one before the experiment can be repeated; for a tube con- 
taining neither air nor vapor affords no protection against superheating, and gives 
no thread of bubbles when the boiling temperature is passed.* 


THE THERMOMETRIC INDICATIONS OF CHEMICAL PURITY. 


Two kinds of tests for chemical purity will be discussed under this head. The 
evidence of homogeneity that.may be furnished by those of the first class is identity 
of the melting- or boiling-point of the original substance with the melting- or boil- 
ing-points of all portions into which a given mass of it may be subdivided by any 
method of fractionation that, without causing decomposition, would naturally 
tend to bring about a difference in the proximate composition of the fractions if 
the substance were a mixture. Tests of this class will be distinguished as “frac- 
tionation tests.” 

Tests of the second class, which it will be convenient to call ‘‘ sharpness tests,” 
depend on the fact that it is rather unusual to meet with mixtures of two or more 
compounds that can be completely melted or distilled within a fraction of a degree 
of the temperature at which fusion or boiling begins, while it is characteristic of pure 
stable compounds to melt or boil at definite temperatures and not between limits. 

The temperature interval between incipient and completed fusion or boiling, 
when measured under fixed conditions, is a definite property of every stable mix- 
ture, which may be given the name of “fusion-interval”’ or “ boiling-interval.”” The 
magnitudes of these “intervals,” in the case of a substance of doubtful chemical 
homogeneity, are often highly significant in their indications. Examples illus- 
trating their interpretation as purity indices are given in the tables on pages 226 
and 227. 

The sharpness tests have the advantage of being applicable to all stable 
substances without any preliminary operations. The fractionation tests involve 
more operations, but when completed are more conclusive. 





* The fact that light glass tubes containing a small chamber for air or vapor at one end 
prevent bumping and promote regular boiling is capable of many applications. With their 
aid even such troublesome liquids as concentrated sulphuric acid and concentrated potash solu- 
tion may be safely boiled in narrow test-tubes, if care is taken never to permit the vapor-chamber 
to fill by a temporary cessation of the boiling. The only precautions necessary to this end are 
to carefully shield the flame and the vessel from drajts of cold air after boiling first begins, and to 
make the vapor-chamber of such a length that it will at all times be entirely covered by the boil- 
ing liquid. Such ebullator-tubes are, like melting-point tubes, best made (cf. p. 219) by 
drawing out large-bore tubes at the blast-lamp. They must be long enough to find support 
against the walls of the flask or test-tube in which they are used, but so thin and light as not 
to endanger its safety. The diameter of the vapor-chamber will generally be 1.5 to 3 mm., 
and its height always less than that of the liquid in which it is to be used. _ If a chamber of 
-gmall diameter becomes accidentally filled, it is most quickly emptied by being passed slowly 

through a flame. It should then be allowed to cool before being used. z 


224 SPECIAL METHODS, APPARATUS, AND REAGENTS, 


Fractionation Tests. 
[For Solids.] 

(1).—Determine the melting-point of the substance. Recrystallize it from some 
volatile solvent in which it is not very soluble in the cold. (Crystallization from 
a hot saturated solution is the most rapid method.) If necessary, concentrate 
the mother-liquors by evaporation. When about three-quarters of the substance 
has been recovered in solid form, collect the crystals all in one portion and drain 
them. Press; dry; and determine the melting-point. If this melting-point 
differs slightly from that obtained before crystallizing, repeat the treatment. If 
it remains unchanged, repeat, using a different solvent. Reject the mother-liquors; 
or unite them and recover the dissolved matter by evaporation. 

If the substance is chemically homogeneous, the melting-points of the several 
successive crystallizations should be identical. If it is a mixture, some constitu- 
ents will probably pass into the mother-liquors more rapidly than others, and the 
melting-points of the several crystallizations will differ. This procedure is almost 
always used when the quantity of substance is very small, and is shorter than the 
method which follows. 

(2).—Prepare a saturated solution of the substance in some chemically inactive 
solvent. By cooling, or by evaporation, crys‘allize out the entire quantity in 
three fractions, of which the middle one (2) should be the largest. Wash, drain, 
and dry the fractions (1) and (8), and determine their melting-points carefully. 
If these two melting-points are identical with that of the original substance (espe- 
cially if they are sharp), the substance is quite probably homogeneous. The test 
may be made more rigorous by recrystallizing each of the end fractions, and deter- 
mining the melting-points of the first crystals separating from fraction (1), and of 
those that separate last from the mother-liquor of fraction (3); or the test sera be 
repeated with other solvents. 

[For Liquids.|;—Distil the substance, if practicable, through a fracon nee 
tower, and collect three fractions, of which the middle one (2) should be the largest. 
Carefully determine the boiling-points of fractions (1) and (3), and compare them 
with that of the original liquid. A more elaborate fractionation is of course 
often necessary. 


Sharpness Tests. 

Three procedures for tests of this class will be given: two for solids, and one 
for liquids. 

(1) —(Fusion-interval for Solids in Capillary Tubes.] 

This procedure is identical with ‘‘The Usual Method for Determining Melt- 
ing-points”’ already described on page 218. The “interval” is the difference 
between the temperature when the first clear droplets can be distinguished on the 
capillary walls, and that at which the substance becomes entirely liquefied. On 
account of its simplicity it is in constant use in organic laboratories; but it is a 
crude method, and in general cannot be depended upon to do more than indicate 
the existence of gross impurity, apparent intervals of more than one degree often 
being obtained in the examination of very pure compounds, even when great pains 
are taken to raise the temperature regularly and slowly. The deficiencies of the 
method are not difficult to explain. The thermometer registers the temperature 


SPECIAL METHODS, APPARATUS, AND REAGENTS, 225 


of the bath, and not that of the melting substance in the capillary. The substance, 
according to its thermal conductivity, heat capacity, state of subdivision, and 
the diameter of the capillary, melts more or less slowly—but, af chemically homoge- 
neous, without changing its temperature. The temperature of the bath and ther- 
mometer are, however, meanwhile slowly but constantly rising. 


(2).—_[Fuston-interval for Solids with Thermometer Immersed in the Melting Sub- 
stance. | 


This procedure has been comparatively little used, but is more satisfactory 
in its results than (1). When the necessary apparatus has once been set up, 
it can be applied to compounds of low melting-point without any special diffi- 
culty. 

The apparatus required is shown in Fig. 8. A is a 
7-inch test-tube, supported within a thin glass air- 
jacket B by cork or asbestos rings CC. Through the 
cork D pass the thermometer # for registering the melt- 
ing-point, an auxiliary thermometer /’ for use in the 
correction for stem-exposure—when this correction is 
necessary—and a light but strong stiff stirrer H. The 
whole arrangement is heated by immersion in a bath of 
water, glycerine, or molten paraffin, contained in a tall 
narrow beaker provided with a stirrer. 

Bring 10 to 15 grams of the dry powdered substance 
into A. Heat the outer bath quickly to a temperature 
10° to 15° higher than that of the melting-point, and 
then hold it nearly constant during the remainder of the 
experiment. Set the inner stirrer in motion as soon as the 
substance melts enough to allow it to be worked freely. 
This will usually be several minutes after the powder 
shows the first signs of shrinkage and softening. Take 
the first reading a minute or two later, when the bulb 
of the thermometer is surrounded by a pasty mass in 
which all interstices are evidently filled by liquid; and continue to record observa- 
tions at intervals of one minute, until not more than one or two centigrams of 
substance remain unfused. About fifteen or twenty readings in all will be made. 
To prevent parallax errors, that would otherwise render the readings nearly worth- 
less, make all observations through the horizontal tube O. A brass cork-borer 
(diameter 5-10 mm.), thrust through a large cork and supported by an iron clamp, 
is an admirable arrangement for the purpose. It has been shown that the 
average of several readings of the same temperature taken in this way by 
practised observers, on thermometers whose degree divisions are 1 mm. in length, 
contains a probable error of only a few hundredths of a degree. 

The jusion-interval in this method is the difference between the means of the 
first and last three accepted observations; or, if there are not more than ten obser- 
vations in a series, between the means of the first and last two observations. The 
first and last reading in a series should, however, always be rejected, if they show a 
considerably more rapid change of temperature during the minute in which they 














Fia. 8. 


226 SPECIAL METHODS, APPARATUS, AND REAGENTS. 


were taken than occurred during other periods of equal length; for such a behavior 
usually indicates that the thermometer has either not been long enough in contact 
with the bath at the beginning of an experiment to acquire its temperature, or 
else that the quantity of solid substance remaining unmelted near the end of the 
test was too small to prevent a measurable rise in temperature in those portions 
of the liquid with which it was not in immediate contact. 

Perfectly pure crystalline compounds that melt without decomposition should 
give an “interval” by this method that is not greater than the unavoidable error 
of observation. The true melting-point of a slightly impure compound may be 
assumed to lie nearest to the higher limit, since impurities cause depression. The 
following table* of fusion-intervals illustrates the kind of information that may 
be derived from the application of this test. 


TABLE OF MELTING-POINTS (CORRECTED) AND FUSION-INTERVALS. 





No Substance. M:; P.(C38) Interval. 
1 Naphthalene, specially purified, 5. 22-12... eee 80-08 0-00 
2 at best commercial’ ".).%.% acs ae eee 79-55 0-20 
3 Benzophenone, specially purified. ................ 47-93 0-06 
4 a +1% OD NG.L. Ue Soe cia oe oe eee 46-83 0-54 
5 Salicylic Acid, good commercials 250.02 aaah ene 157-81 0-04 
6 Thymol “ie os el sts te alate ini en pene 49-51 0-21 
° Stearic Acid, soldias#2G(P." a0 ees s ce eee 63-7 2-8 
8 es ‘« (once recryst. from Alcohol)........... 65-65 1-70 
9 i ‘SS (iwice a ee POE ERS SRP Leas ans 67-80 0-80 

10 Sis ‘SP (thrice mare ed PER remere  > - 68-80 0-00 
i Cane-sugar Crystals (melts with decomposition) .... 153-8 (?) 8-8 (2) 


(3).—[Sharpness Test for Liquids.] 

Distil 5-8 cc. of the liquid from a 10-15 ce. (or larger) distilling-flask, with all 
the precautions mentioned in the directions given for boiling-point determinations 
on page 221, recording thermometer readings at intervals of one minute. The 
readings must be made through a narrow horizontal tube, mounted and used as 
in the determination of the fusion-interval (cf. Fig. 8, page 225). The “‘boiling- 
interval” will be the difference between the mean values of the first two and the 
last two significant readings. 

Results by this method are of the same order of reliability as those for the 
fusion-interval by procedure 2, but are so much more easily obtained that pro- 
cedure 3 is of far greater practical importance. The significance that may be 
safely attached to boiling-intervals in special cases will be best understood from 
an inspection of the following table, in which a considerable number of such data 
obtained from typical pure and commercial preparations and mixtures have been 
collected. 


* The results in this table, as well as those on the boiling-interval on page 227, were obtained 
by Mr. Arthur Davis in the author’s laboratory, by the use of a 360° thermometer, the length 
of whose degree was slightly less than one millimeter. The last significant figure in all these 
results was secured by the process of averaging, and has a probable error of about three units. 

Substances 1 and 3 had been brought to a condition of exceptional purity by distillation 
and repeated recrystallization from alcohol. Their behavior is that of the typical, pure stable 
compound. 2 and 4 illustrate the effect of slight impurity in the case of the same substances. 
2, 5, and 6 are good examples of what may be expected from high-grade commercial prepara- 
tions of good stability. 11 shows the uselessness of sharpness tests for pure compounds that 
decompose noticeably in melting. Numbers 7-10 show the progressive changes in the inter- 
val that occur in the crystallization of an impure substance by a suitable method. 


SPECIAL METHODS, APPARATUS, AND REAGENTS. 227. 


TABLE OF BOILING-INTERVALS OF TYPICAL COMPOUNDS AND MIXTURES 
ILLUSTRATING PROCEDURE (3). 








Boiling- 
Substance. interval 
deny 
a _ rm 


Meee eres pecially DPUTIfied . . 5...) e eens cece cceccdvecwevccecndiesesecses 
Bempemtemere emt o biiophene, ““frozen’”’. .......5.-00ccccancceccescceuvecevas 
MR COILIDANIN'S. oe ec ce cee ccc ccuccauvceccuutessesven 
REPO ETS ADL AUIN Ss... oo. oc ace vp wee hac tleuweelcdalecccteaecencncncs 
Meee commeuewmerck < from cryst. Benzene... .......0..cseccceucucscceccceces 
8 : PUMUpercialt rade steag nicer ewe hh ete ai ee ag a acs 
iimiecnysamiuine, MMerck’s, free from mono compound ............-ss«sesseceress 
; COCUIREr CIAL STOUG. ba. Wat, femme, eee Mea: A eS 
EES i Se ge en ae oy ee re 
eee rad ene Disulphite compound .... cc. s ses ce cere ede cc ececwcvcecacs 
Ei Bee omenciucally pure,” Merck’s.... <2 5 scence cov hatha sc cantseaen boc 
NO yo en otic hee ba cele pg be mau cubnaeannwes 
Bete eatin s intermediate grade.. .... 22... lec ee ces enc cuccccuceuvceness 
SMES VGICHIC oo ye ol cet ee nee dec sade ewgeeececnsunacectusen 
MMMM TUTE ALUT Sos a hed ele ee cate nv Viable ve dwsnveucenuvaees 
RR SIRLOIN Sous. ke a ne gale avis ee wuss o Ue cad v omens eravnadecs 
benzildenyde, originally “C. P.,” but slightly oxidized. ...........cenenevceess 
Piemmeacede sicic, containing about 2% water. .............ccerecccecvceeces 
Acetoacetic Ether, Kahlbaum’s (boiled with some decomposition) ............... 
Pennemenncia, Merck’s (boiled with decomposition)...............-cccvcccnes 


Piavenceraie, Kahlbaum’s, a mixture of isomers... ...0...... 00 0c veces cece aeas 70 
Ethyl Ether, commercial, US. P., containing much alcohol and water........... 40-85 
Semen eeatrnrry 7 LOWENC. |... oe ee a gi da vee cnc cdo w eile sccceansues 32 


Nimovenzene conwmining 57%, o-Nitrotoluene.... 0.0... ccc cece cnc c ence ncccees 
eee eee enuaraine 57, Methyl Alcohol... 2... 2.0.06. ce cn cn eee ccd weeweneeedes 
emer oman contaming 5% o-Toluidine... ........2-2.ece ee eccees Loe bates 
‘*Constant-boiling Mixture” of Methyl Alcohol and Benzene *................... 


CAOONOCWWWNFRRrRooOoococoocoocococooc°ce 
oe one 
(Je) 





SPECIFIC GRAVITIES. 


The specific gravity of solid organic compounds has been determined for com- 
paratively few species, and is consequently not at present a property of great 
analytical importance. The specific gravity of liquid compounds, on the con- 
trary, has been determined with almost the same regularity as the boiling-point, 
and sometimes affords the simplest possible means for the arrangement of such 
species into “‘Sections.”’ The recorded values for the specific gravities of organic 
liquids are usually reliable in the second decimal place, often in the third, but very 
rarely in the fourth. 

As the analyst willoften have too little of a pure compound to enable the deter- 
mination of its specific gravity by the Westphal balance or hydrometer, two other 
methods for the determination, which are also rapid and usually sufficiently accu- 
rate for his purpose, will now be described in detail. . 





* Ryland, Am. 22, 384 [1899].—This mixture is an example of many known cases of two 
miscible liquids, that, when once brought together in certain proportions, boil like a pure com- 
pound, and can not be separated by the usual method of fractional distillation. The analyst 
is not very likely to meet such mixtures ready formed in commercial preparations, the chances 
all favoring .the presence in excess of some one constituent. He may, however, somtimes pre- 
pare such mixtures for himself, while attempting to resolve a mixture into its constituents by 
fractional distillation. Such mixtures have a constant boiling-point only under the atmos- 
pheric pressure at which they were prepared, so that the absence of homogeneity may be detected 
by distilling over one half im vacuo and then determining the boiling-interval under the ordi- 
nary pressure of what remains in the flask—provided both constituents do not nave the same 
vapor-tension at all temperatures, which is a coincidence that is very unlikely to occur. 


228 SPECIAL METHODS, APPARATUS, AND REAGENTS. 


Determination of the Specific Gravity of Small Quantities of Liquids. 


(1).—[Method for 0.20 cc. of Substance.] 

Prepare a pycnometer for this purpose by bending a piece of thick-walled 
glass tubing 28-30 cm. in length, into the form shown in Fig. 9. The tubing 
should be of the kind used in gas analysis 
for transferring gases from one container to 
another, and have an internal diameter of 
1 mm. and an external diameter of about 
5mm. The part between A and B should 
be drawn out to form a narrow-bored but 
thick-walled capillary,8 cm.long. The zero- 
point of the instrument is a short, thin hori- 
’ gontal scratch made at C. 

To calibrate the pycnometer begin by 
attaching a few centimeters of clean rubber 
tubing at D. Slip the point of an ordinary 
medicine-dropper M into the open end of 

mas Os the rubber tube, and then a light brass 
burette-clip over the latter, so that it may be quickly clamped off at any time at 
D. Next incline the instrument as shown in the figure, so as to immerse the point 
of the capillary in cold water contained in a 3-inch test-tube. The manipulation 
will be facilitated by having the test-tube held in a clamp. Open the clip at D. 
Compress the rubber bulb of the dropper to expel air. Then allow the bulb to 
expand slowly again, so as to suck water into the pycnometer. When the latter 
has filled to the horizontal arm above the zero-mark, close the clamp. Separate 
the dropper from the rubber tube. Then take off the clamp and separate the 
rubber tube from the pycnometer. Next suspend the pycnometer for some time 
in the air from the hook of the analytical balance, or for five minutes in a beaker 
containing cold water having the desired temperature. When the instrument and 
its contents have acquired the temperature of their surroundings, touch the edge 
of a bit of dry filter-paper to the tip of the capillary A, which must be filled by 
the water. As the water is absorbed by the paper, its level in the longer arm of 
the pycnometer will gradually fall. Bring this level exactly to the zero-mark. 
{If care is taken in subsequent operations not to incline the capillary AB much 
below a horizontal position, no water will flow out.|—The pycnometer is now ready 
to be weighed, unless it has been suspended in water, in which case it must first be 
carefully wiped dry. 

To determine a specific gravity by this method, fill the pyenometer with the 
organic liquid by the manipulations described above in connection with the cali- 
bration. If we then represent the weight of water required to fill the instrument 
to the reference-mark by w, and the weight of the same volume of the organic 





compound by 0, the specific gravity, uncorrected for temperature, will be —. The 


result should not differ from the true gravity by a full unit in the second decimal 
place. 

After use, the pycnometer should be washed out at once with alcohol or ether, 
and thoroughly dried by an aspirated current of dry air. When not in use, it 


SPECIAL METHODS, APPARATUS, AND REAGENTS. 229 


should be kept in a clean box along with a carefully adjusted counterpoise made 
from thick sheet lead, and a card giving the weight of water which it contains at 
the room temperature. As long as the counterpoise continues to balance the dry 
piknometer, its capacity may be assumed to have undergone no change. 
(2).—[Method with 1 cc. Pipette.] 

This very rapid method has an accuracy limit of about a unit in the third deci- 
mal place. 

Calibrate a pipette (A in Fig. 10), to contain (not deliver) one cubic centi- 
meter when filled to the reference-mark. If the determinations are to be made at 
about 20°, scratch the reference-mark on the pipette stem 
at the level of the lowest point of the meniscus seen when 
the pipette contains 0.9982 grm.* of distilled water at that 
temperature. Then the weight in grams of any liquid 
having the same volume at 20° will be the number express- 
ing its specific gravity at 20°/4°. 

The pipette is to be manipulated as follows: Suck in 
the liquid until it stands about half a centimeter above the 
reference-mark. Wipe off any traces of the liquid adher- 
ing to the outside of the stem. Then allow it to run out 
until the meniscus just touches the reference-mark. Wipe 
off the fraction of the last drop that hangs from the nar- 
row outlet of the pipette, by touching it with the finger. 
Stand the pipette in the recipient tube B. Support the 
apparatus by the aid of the attached platinum wire on the 
balance-pan, as shown in the cut, and weigh at once. If 
an accurately adjusted lead counterpoise for the entire 
apparatus is kept in readiness and placed upon the oppo- 
site pan of the balance, the weights that have to be added 
to produce equilibrium give the desired gravity directly without any calculation. 





* The correct location for this mark is most easily ascertained (as suggested in Ostwald’s 
‘“Physico-chemical Measurements”) by gumming a strip of millimeter-paper to the stem of 
the pipette and determining the weight of water corresponding to two points on the scale, one 
on each side of the true position and 10 mm. apart. ‘‘Then, on the justifiable assumption that 
the stem is cylindrical throughout this short piece, we can calculate the proper position of the 
mark from these two weighings.’’ If, for instance, one weighing is 1-0222, the other 0-9930, 


and the desired weight 0-9982, then the reference-mark should lie sae cake aS x10=8-3 mm. 


1-0222—0-9930 
below the upper mark on the paper scale. 
If it is desired to calibrate the pipette for use in comparing the density of a liquid at some 
other temperature than 20° with that of water at 4°, the proper weight of water to be used 
may be taken from the accompanying table of the density of water at various temperatures. 


DENSITY OF WATER BETWEEN 15° AND 30°. 





a 









Tempera- Densities. Tempera- Densities. Tempera- Densities. 
ture (C.°). ture (C.°). ture (C.°). 
15 0-9991 21 0-9980 26 0-9968 
16 0-9990 22 0-9978 va 0-9965 
‘a 0-9988 20 0-9976 28 ‘| 00-9963 
18 0-9986 24 0-9973 29 0-9960 


19 0-9984 25 _ 0:-9971 30 0-9957 












230 SPECIAL METHODS, APPARATUS AND REAGENTS. 


COLOR. 


According to Aubert there are at least one thousand hues in the solar spectrum 
which may be distinguished by the human eye as different. Each of these hues 
“may again be varied many times by changes in luminosity and admixture with 
white light, giving in the aggregate, it 1s estimated, as many as two million color 
differences that are recognizable under favorable circumstances. Yet, although 
the color of a chemical compound is often its most salient physical property, and 
the changes which this color experiences when treated with reagents may furnish 
the simplest test that can be applied for its identification, careful analysts have 
always very properly refused to attach the same importance to verbal descriptions 
of subjective color phenomena as a means for specific characterization, that they 
willingly grant to the recorded values of melting-points, boiling-points, specific 
gravities, and other physical constants whose determination requires the use of 
comparatively slow and elaborate methods of measurement. 

The chief causes for the disrepute into which color tests have fallen are: the 
customary failure, except in spectroscopic work, to refer colors to any well-defined 
standard; the loose use made of the terms constituting the popular nomenclature 
of color; the imperfect development of the color memory; and, finally, the fre- 
quent omission of minor but essential experimental details from the directions 
given for the performance of color reactions. To minimize these defects in the 
original color descriptions and tests of this work, it has been considered desirable, 
whenever possible, to consistently adhere to a more definite color terminology 
than has before been used for chemical purposes. It has been necessary, how- 
ever, to leave all copied color descriptions recorded in terms of the crude popular 
standard in which they were found; i.e.a standard in which red might signify any- 
thing from violet-red to orange, or from pink to russet. 

The Terminology of Color.—To prevent possible misunderstandings, before 
proceeding to the subject of color comparisons, it will be necessary to define the 
sense in which certain common color terms will be used. It should be remarked 
that the restricted meanings that will be accepted for the terms have the sanction 
of good authority, though they are sometimes used popularly, and by artists, with 
very different meanings. 

A Pure, Full, or Saturated Color is the most intense expression of that color 
without admixture of white, black, or gray. 

No pigmentary color is absolutely pure. A surface painted with artificial 
ultramarine blue, for example, reflects with the blue about 25 per cent of white 
light, the effect of which is to soften the color and reduce its action on the eye. 
In the color-standard cards A and B in the back of this volume, the third hori- 
zontal series of color rectangles, counting from the top of the sheet, approach most 
nearly to the corresponding colors of the spectrum; and, as the pigmentary types 
of the pure colors, will sometimes be referred to as the ‘“‘pure”’ or “‘full-color series”’ 
of the standard. 

The Luminosity of a color is that constant of it which is dependent on the 
quantity of light which it transmits to the eye, and is nearly equivalent to bright- 
ness. Two colors may be equal in purity, each reflecting, we will say, 75 per cent 


SPECIAL METHODS, APPARATUS, AND REAGENTS. 231 


of blue and 25 per cent of white light, but can not be made to match except by 
exposing the brighter surface to a feebler illumination than the other. 

The Hue of a color is in some respects its most fundamental quality. It is 
dependent entirely on the refrangibility, or wave length, of the kinds of light pro- 
ducing the sensation. The purity and luminosity of colors may be absolutely equal, 
but one may appear red and the other yellow. The difference is one of hue. Each 
color in the standard, in going from red to violet, is a distinct hue. 

A Tint of a color is the result obtained by reducing a pure or full color by the 
addition of white light. In the standard, the two color rectangles immediately 
over each full color are its ‘‘tints.”” Tint 1 contains less white than Tint 2. Tint 3, 
which is sometimes referred to in descriptions, is not a tint actually represented in 
the standard, but is to be imagined as a tint of about half the saturation of Tint 2. 

A Shade of a color is the result obtained upon viewing a full color in shadow. 
With pigments, shades of most colors are obtained by adding black. The two 
shades corresponding to each full color of the standard are placed vertically under it. 

Each of the upper five colors in the same vertical column of the standard— 
two tints, two shades, and one full color—is called a tone of that particular color 
scale. The full color of the scale is sometimes called the ‘‘normal tone”’ of the 
color. 

A Broken Color is the subdued effect obtained by mixing a full color with 
neutral gray (black and white), viewing the tint of a color in a shadow, or a shade 
of a color in strong sunlight. The lowest horizontal series of colors in each of 
the sheets of the standard contains ‘‘medium”’ tones of the broken colors. Tints 
and shades of these ‘‘medium tones’’ will sometimes be referred to in the text as 
“light” or “dark” broken colors, respectively. It has not been considered necessary 
to represent them on the color sheets. The russets, browns, citrenes, and olives, 
are typical broken colors. All pigmentary colors, including the so-called full-color 
series of the standard, are somewhat broken; and in many color reactions, partic- 
ularly where intense violets are under observation, it will be found that the colors 
to be compared are distinctly more saturated than the purest corresponding color 
of the standard. This will not often prevent the recognition of the fundamental 
hue of the color, however. 

The Use of Pigmentary Color Standards.—Every colored substance illumi- 
nated by ordinary daylight owes its color to its selective absorption of rays of 
certain definite wave lengths from the white light that penetrates its surface. The 
light that escapes absorption and is transmitted to the eye is, almost without 
exception, a mixture of rays of many different wave lengths together with more 
or less unchanged white light. The subjective effect is, however, the perception 
of a simple color. Red and yellowish-green lights, for instance, give an orange 
which looks in all respects like the orange of the spectrum. Unaided by the spec- 
troscope, it is impossible for the eye to detect in it the presence of either red or 
yellowish green. In the same way the original ingredients of every subjective 
color entirely elude visual analysis, and it is therefore theoretically possible, by 
the use of a suitable mixture of pigments, to prepare a systematically graduated 
scale of apparently homogeneous colors, that may be used as a color standard, 
and with which all other subjective colors, however simple or complex the light 


232 SPECIAL METHODS, APPARATUS, AND REAGENTS. 


rays producing them may be, can be compared. As the colors of all natural 
objects are somewhat “‘broken,” the fact that the colors of pigmentary standards 
are less “‘saturated”’ than the corresponding hues of the spectrum, is often an 
advantage rather than otherwise, and in other cases merely limits, but does not 
destroy, their usefulness. 

The exact color descriptions of this work are all expressed in terms of the 
Bradley Color Standard. This standard, mounted in a special compact form, 
to facilitate its use in the laboratory, will be found on the two cards,* A and B, 
in a pocket in the back cover of this volume. It contains eighteen pure colors; 
and of derived tones, thirty-six tints, thirty-six shades, and twelve medium 
broken colors. | 

Color Symbols are only used in the tables for describing such colors as have 
been actually compared with the Bradley Standard in the author’s laboratory. 
These symbols are as follows: 

R=RED; OR=ORANGE-RED; RO=RED-ORANGE; O= 
ORANGE; YO=YELLOW-ORANGE; OY=ORANGE-YELLOW; 
Y=YELLOW; GY=GREEN-YELLOW; YG=YELLOW-GREEN; 
G=GREEN; BG= BLUE-GREEN; GB=GREEN-BLUE; B= 


BLUE; VB=VIOLET-BLUE; BV=BLUE-VIOLET; V=VIOLET; 
RV=RED-VIOLET; VR=VIOLET-RED. 


The Tints of any color are represented by the symbol of the normal tone of 
the color followed by the symbol T1, T2, or T3; in which the numeral stands for 
the number of the tint, Tint 1 coming next to the normal tone of the color in satu- 
ration. The Shades of a color are in like manner represented by adding S1, or 
$2, to the symbol of the normal tone. 

The following examples will illustrate the use of these color symbols: YS2= 
the second shade of yellow; YT1=the first tint of yellow; OT1I-OYT1=a color 
between the first tint of orange and the first tint of orange-yellow. 

Comparisons with the Color Standard.—All comparisons with the Standard 
should be made near an unscreened window through which light reflected from 
the sky—not direct sunlight—falls upon the colored object and standard from 
behind the observer. 


* The colors used on these sheets are those of the Bradley Standard, as described in Milton 
Bradley’s “‘Elementary Color”, (Springfield, Mass.). The fundamental colors, red, orange, 
yellow, green, blue, and violet are claimed to be careful pigmentary imitations of the hues 
seen at certain definite points in the solar spectrum. The wave lengths of the light emitted 
by the portions of the spectrum selected for imitation are, according to the measurements of 
Prof. A. H. Pillsbury: 6571 for red; 6085 for orange; 5793 for yellow; 5164 for green; 4695 for 
blue; and 4210 for violet. This series of six fundamental normal hues is increased to eighteen, 
by introducing twelve additional colors in such a way as to bring two new hues, separated by 
equal chromatic intervals, between each of the original colors. The values for these inter- 
mediate hues were determined, by blending the adjacent hues of the original series of six in 
pairs, by Maxwell’s method, on a rotating color-wheel on which the areas of the two colored 
sectors were in the ratio of two to one. Yellow-orange, for example, is the subjective color 
resulting from the blending in the eye of the light from two superficial units of the funda- 
mental orange and one of the yellow; orange-yellow, of two parts of the yellow and one of 
the orange. Two “tints” and two “shades” were then derived for each of the eighteen ‘‘ normal 
tones” by dilution with white or black. 

Additional copies of these color sheets, to replace the originals as they become soiled or 
injured, can be procured at any time from Messrs. John Wiley & Sons, the publishers of this 
volume. A comparison of the new color sheets with well-preserved samples of the Bradley colored 
papers prepared at different times during the last dozen years, indicates that the colors used are 
stable, and that much care has always been taken by the manufacturers to faithfully reproduce 
the colors of their first standard. 


SPECIAL METHODS, APPARATUS, AND REAGENTS. 233 


If the substance is a solid, it should be placed upon a piece of white paper, 
and laid upon the perforated shield accompanying the Standard, close to the rect- 
angular window. ‘The object of the screen is, partly to protect the Standard from 
accidental injury, and partly to prevent the confusion that is apt to arise from 
presenting many kinds of colored light to the eye at the same time. It is impor- 
tant to remember in color descriptions, that the color of a solid substance in masses 
is often different from its “streak,” or color of its fine powder; and that the color 
of a moist precipitate is usually different from that of the same substance after 
drying. It is only occasionally that a color is met with which exactly matches 
one of the color squares of the Standard. The statement in descriptions, that a 
compound has a light orange-yellow color (YOT1), is therefore to be understood 
to mean nothing more than that its color more closely resembles this color of the 
Standard than any other. If the color to be described obviously lies between two 
colors of the Standard, the fact is, however, often indicated by the symbol; e.g. 
YOT-OYT1. 

To examine a solution, lay the perforated screen upon the Standard so as 
to expose to view one or two color patches that resemble the color to be described, 
and hold or support it in an upright position, so that diffused sky light, coming 
from behind the observer, will fall upon it. Then hold the test-tube containing 
the solution vertically in front of the shield at a distance of about twice or thrice 
its diameter, and just above or to one side of the perforation. The comparison 
will thus be made by transmitted white light reflected through the solution from 
the screen. In observing the color of a fluorescence, replace the white screen by 
one coated with lamp-black. The light reaching the eye is in this case reflected 
back from the solution and not from the screen. 

The color of a solution depends not only upon the nature of the substances 
dissolved, but also upon its concentration, the thickness of the colored layer, and 
sometimes upon the temperature. No description of an unfamiliar color reac- 
tion in a solution is entirely satisfactory unless all these conditions are given. In 
the greater number of cases, it is true, the result of dilution is chiefly to reduce 
the saturation of the original color; i.e., to produce a lighter tint of the original hue. 
But some change in hue is of very common occurrence, and in tests, like that for 
acrolein (Test 112), where the change in hue upon continued dilution with water 
is from orange-yellow to violet-blue, it is the most striking and essential feature 
of the test. 

The temperature is sometimes a very important condition, as in Test 401 for 
phenols with ferric chloride, where a pronounced yellow color is communicated to 
the solution in blank experiments by the reagent alone, unless the test is made 
cold. Unless otherwise indicated by the context, all color comparisons with solu- 
tions which are referred to the color standard in this work relate to solutions of 
approximately definite concentration, the colors being observed, as above stated, 
in three- to six-inch test-tubes at the temperature of the laboratory. Many color 
reactions, especially among those with ferric chloride for the phenols, and for the 
Species of Suborder II, Division A, Section 2, give colors which change rapidly 
on standing. In the absence of directions to the contrary, such colors should 
always be observed as soon as possible after their appearance. 


234 SPECIAL METHODS, APPARATUS, AND REAGENTS. 


It is more difficult to match the colors of solutions with a pigmentary stand- 
ard than those of solids; for the colors in the Standard often appear distinctly 
“broken”? and muddy by contrast, particularly if the solution happens to be a 
brilliant purple. But the fundamental hue, which is the most important color 
element, will still usually be distinguishable. Such comparisons are sometimes 
facilitated by using a solution of the colored substance so dilute that it will approxi- 
mately match the first ‘‘ tint” of a hue, rather than the ‘“‘full”’ or “‘normal”’ color of 
the scale. 


THE MANIPULATION OF SMALL QUANTITIES. 


As has been stated on page 2, most of the specific tests in this volume depend- 
ing upon the isolation of a pure derivative of a compound, are made with only a 
decigram or less of substance. The use of these small quantities not only saves 
valuable material, but also greatly shortens the time required to complete an 
experiment; so that,in many instances, a derivative may be prepared, filtered 
off, washed, recrystallized, and dried ready for a melting-point determination 
within half an hour. Some of the conditions and expedients that have been found 
conducive to success in such preparations in the small way deserve special mention. 

Solid Precipitates.—In making the selection of a characteristic solid deriva- 
tive suitable for preparation on the small scale in specific tests, it is desirable to 
choose one that will separate in a bulky but crystalline condition from the solvents 
used; and which may be recrystallized quickly by cooling its hot saturated solu- 
tions. Precipitates that are both crystalline and voluminous may be removed 
from glass surfaces and filters, and washed, recrystallized, dried, and handled 
with much less loss than those that are either too compact, slimy, or gelatinous. 

Precipitates that are very soluble in the cold, and which form only after evap- 
oration of a considerable portion of the solvent, are poorly adapted for these tests; 
evaporation being a slow operation, and the difficulty in separating crystals that 
are uncontaminated by by-products from the small mother-liquor being usually 
greater than in the method by cooling. Among the numbered specific tests are 
many examples of derivatives that combine all the good qualities just mentioned in 
a high degree. A single decigram of some of the aromatic nitro-derivatives, for 
example, upon separating from a hot saturated solution in dilute alcohol, is sufficient 
to fill entirely a five-inch test-tube with a mass of hard interlacing crystals. Some 
sticky resinous precipitates of equal weight would be entirely lost as inconspicuous 
adhesive smears on the test-tubes or filters. 

If no precipitate should appear upon cooling what is supposed to be a hot 
saturated solution of a solid derivative, always close the mouth of the test-tube 
firmly with the thumb, and shake vigorously and persistently. Many compounds 
whose preparation is directed in the numbered specific tests, tend to form super- 
saturated solutions; but upon being thus treated, give bulky crystalline precipi- 
tates. This final precautionary shaking should never be omitted. 

Small precipitates should be collected on correspondingly small filters and 
funnels. A large filter retains so much mother-liquor as to require excessive wash- 
ing; and the precipitate, if at all adhesive, will be very difficult to separate from 
the large paper surface. A supply of cut filters, 5 cm. in diameter, and a 


SPECIAL METHODS, APPARATUS, AND REAGENTS. 235 


few very small funnels are therefore indispensable for the performance of the 
specific tests. 

When hot filtration of a saturated solution is necessary, the funnel and filter 
are most easily and effectively heated by first pouring through them some of the 
boiling liquid that is to be used as the solvent in the experiment. Clogging of 
the funnel-tube by separation of solid matter may be prevented by cutting off 
its lower end so that only about 1 cm. remains. If the solid begins to crystallize 
out at a temperature very little below the boiling-point of the solvent, a com- 
paratively large filter and funnel are to be preferred to a small one, as they will 
give more rapid filtration. On a very small filter there is greater danger that the 
free passage of the solution may become obstructed by the deposition of solid 
matter in the pores of the paper. 

In filtering from one test-tube into another, hang a short piece of thick bent 
copper wire over the lip of the test-tube in which the funnel is placed, so as to 
leave a passage for the escape of air from the tube. For mixtures that filter 
slowly, fit the recipient test-tube with a doubly perforated rubber stopper and 
use it as a filter-bottle, placing a small filter-cone in the funnel and applying gentle 
suction with the filter-pump. 

In washing small precipitates with a liquid in which they are rather soluble, 
the danger of using an unnecessarily large volume of solvent has been provided 
against in the more important procedures by the specification of some definite 
volume. These directions should be closely followed. The solvent should be 
dropped upon the precipitate in such a manner as to detach it from the sides of 
the filter and wash it down into the point, so as to facilitate its subsequent separa- 
tion from the paper. Very small precipitates which do not require much washing, 
and which it is thought undesirable to bring upon a filter, may be separated from 
most of the supernatant solution by decantation, and then shaken out upon a piece 
of porous tile. When the adhering solution has disappeared in the tile, 1t may 
be sprayed or moistened as many times as desired with the solvent, waiting after 
each treatment until the liquid disappears before adding more. 

If it becomes necessary to redissolve a precipitate that is very small and firmly. 
attached to the filter, open the filter, tear off the sector to which the solid adheres, 
and boil it with the solvent. Do not boil up the whole filter, or the pulpy mass 
formed may cause explosive boiling and loss of the substance. 

Precipitates whose melting-points are not too low are directed to be dried in 
a drying-oven at some definite temperature and for a definite time. Solids of 
very low melting-point are air-dried at the ordinary temperature, or supported in 
a warm place over a drying-oven, on a piece of porous tile or filter-paper. Drying 
in the oven should always be preceded by rubbing the moist substance over the 
surface of a porous tile with a small spatula, or pressing it between filter-paper 
to remove all the mother-liquor. 

Liquids.—The preparation of liquid derivatives is not often recommended in 
specific tests, because the purification of such compounds on the small scale gen- 
erally presents special difficulties. The procedure for the isolation and identifica- 
tion of liquid alcohols from the saponification of a gram or two of an ester (p. 114), 
the Siwoloboff boiling-point method for two or three drops of liquid (p. 222), and 


¢ 


236 SPECIAL METHODS, APPARATUS, AND REAGENTS. 


the method of page 228 for the determination of the specific gravity of liquids having 
a volume of only 0.2 cc., are, however, examples which show that the difficulties 
connected with the manipulation of small quantities of liquids may sometimes be 
satisfactorily overcome. ‘Test-tube experiments with less than a centimeter of a 
liquid must be made in very narrow tubes. With a tube of 5 mm. internal diam- 
eter, five drops of a substance are all that is required to enable a satisfactory obser- 
vation of the action of sodium on alcohols in Test VIII-2. 

The separation of very small volumes of two liquids of different specific gravi- 
ties is best made with a pipette. The mixture is placed in a narrow test-tube, 
and all but a few drops of the substance that is present in the greater quantity 
are removed by a large pipette and rejected. The remainder of the liquid, meas- 
uring perhaps 1 cc., is then sucked up into a small pipette made from a piece of 
glass tubing that has been drawn out so as to have an average internal diameter 
of only about 2 mm. in the long tapering portion. The suction is 
most easily controlled if applied by the rubber nipple of a medicine- 
dropper. When both liquids have been brought into the pipette, and 
appear in two layers after standing, they may be separated to a 
fraction of a drop by slowly ejecting them, successively, into separate 
tubes. 

The most perfect control over the rate of flow in careful experi- 
ments is gained by the employment of the safety pipette shown in 
Fig. 11. This pipette is provided with a regulator A, 3 cm. in length, 
made by drawing out a piece of thermometer tubing at the blast-lamp 
until the capillary at B and C is narrowed almost to complete closure; 
and then cementing it with melted wax, D, into a short section of glass 
tube of the same diameter as the upper part of the pipette stem. The 
capillary, if sufficiently constricted, offers so much resistance to the 
passage of gas from the air-space, E to H, that the contents of the 
pipette can not be discharged in less than several seconds, even when 
the bulb is suddenly and forcibly compressed. By the use of this 
device the transfer of a small measured volume of a valuable or corro- 
sive liquid in work at the balance (as in weighing out acetic anhydride for Test 
VIII-3) is made a safe and simple operation. 





Fig. 11. 


SPECIAL REAGENTS. 


The following is a complete list of the less common chemicals and solutions 
required for the performance of the. ordinal, generic, sectional, and numbered 
specific tests of this volume. All these reagents can be purchased, or easily pre- 
pared by following the directions given in these pages. Most of them are already 
used in analytical laboratories. 


[For Ordinal Tests.] 


Metallic Sodium. The best commercial sodium, free from particles of salt. 
Sodium Nitroprusside. In small crystals or powdered. 

Nitrosylsulphuric Acid. Preparation described on page 13. 

Fluorescein Paper. Preparation described on page 14. 


SPECIAL METHODS, APPARATUS, AND REAGENTS. 237 


[For Generic Tests.] 


Fuchsine Aldehyde Reagent. Preparation described on page 15. 

a-Naphthol Solution. A 10 per cent solution in chloroform. See page 26. 

Decinormal Sodium Hydroxide (aqueous) 

Decinormal Hydrochloric Acid (aqueous) Carefully standardized. 

Normal Sodium Hydroxide (aqueous) 

Normal Sulphuric Acid (aqueous) 

Approximately Normal Sodium Hydroxide (alcoholic). Unless the alcohol is very free from 
aldehyde it will become colored on keeping, and hence should not be prepared in large 

iii quantities. 

Phenolphthalein. A 1 : 300 solution in 50 per cent alcohol. 

Ferric-Chloride Solution, A 10 per cent aqueous solution made from the sublimed chloride. 

Hydroxylamine-hydrochloride Solution. Prepared as described on page 133. 

Alcoholic Sodium-hydroxide Solution for Test VII, A. Prepared as described on page 133. 

Phenylhydrazine. Redistilled if the color is not very light. 

Acetic Anhydride. 


[For Sectional Tests.] 
Phenylhydrazine Hydrochloride. Prepared as described on page 32. 
Fehling’s Solution. Prepared as described on page 33. 
Bromine Solution. 2 cc. bromine in 50 cc. dry carbon tetrachloride. See page 195. 
Fuming Sulphuric Acid. An acid of sp. gr. 1.89, which may be prepared by dissolving sulphur 
trioxide or a solid Nordhausen acid in oil of vitriol. 
Fuming Nitric Acid. Specific gravity 1.48. 


[For Occasional Use in Numbered Specific Tests.] 


Acetyl Chloride. 

Aluminium Chloride. Dry, sublimed. 

Ammoniacal Silver-nitrate Solution. Prepared as described on page 22. 

Si amaan Cuprous-chloride Solution. Prepared as described on page 197. 
ine. 

Benzaldehyde. 

Benzoyl Chloride. 

Bromine. 

Chromic Anhydride. 

3, 5-Dinitrobenzoic Acid. Prepared by Kahlbaum, and for sale by dealers. 

Iodine Solution. Prepared as described on page 166. 

Mercuric Oxide. 

6-Naphthol. 

Phosphorus Pentachloride. 

Phlorogiucin Solution. Prepared as described on page 33. 

Resorcin. 

Para-toluidine. 


SPECIAL APPARATUS. 


Ignition-tubes of Hard Glass or Iron. Description and cut on page 10. 

Asbestos-board Screens. Size 4”x4”. Thickness 36”. Used in the sodium fusion (page 10, 
Fig. 1); the determination of boiling-points (page 221, Fig. 6); and in specific tests (e.g., 
Test 311-2). 

“*Medicine-droppers.”? As shown in Fig. 1, page 10. 

Lipped Test-tubes. In addition to the usual assortment of test-tubes of the larger sizes, a good 
supply of tubes with a height of 3 inches and diameter of 4 inch, with cork stoppers to 
fit, and a few with a height of 3 inches and diameter of 3, inch, should always be kept 
in readiness. (Cf. page 112, Fig. 3, and page 152, Fig. 4.) 

Mounted Burettes for Decinormal and Normal Alkali and Acid. Mounting shown in Fig. 2, page 78. 

Pipettes with Bulbs and Long Stems. Of the usual pattern and calibrated to deliver 2 cc., 25 ec., 
and 50 cc., respectively. 

I-cc. Pipette Graduated to Hundredths. Straight, without bulb; graduated by the manufacturer. 

1-cc. Pipette for Specific Gravities. Page 229, Fig. 10. 

1o-cc. Graduated Cylinders. With lip and foot for general use in rough measurements. Gradu- 
ation to half centimeter. 

Capillary Piknometer. Page 228, Fig. 9. 

Safety Pipette. Description on page 236, Fig. 11. : ‘ 

Covered Heating-bath. Page 152, Fig. 4. Recommended for use in several generic tests. 

Bath for Melting-point Determinations. Page 218, Fig. 5. 

Melting-point and Ebullator Capillaries. Pages 219 and 222, Fig. 7. xe 

Apparatus for Determination of True Melting-point and Fusion Intervals. Page 225, Fig. 8. 

Glass Funnels. Diameter 2 cm. 

Cut Paper Filters. Diameters 3 cm. and 5 cm. 


a 











ALPHABETICAL INDEX. 


The alphabeticai index relates primarily to classification, analytical methods, numbered tests, reagents, 
and apparatus, but also contains the names of such compounds—about 15 per cent of the total number 
described—as will be most frequently sought in the tables. To find the description of any compound of minor 
importance, consult the complete ‘‘Formula Index” on page 244, 


A 


Abbreviations, table of, xi 
Abietic acid, 63 
Absinthin, 206 
Acenaphthene, 200 
Acetal, 19 
behavior in Test U 16 
Acenaphthene, 209 
Acetal, 19 
Acetaldehyde, 22 
Acetic acid, 80 
Acetic anhydride, 73 
Acetone, 148, 144 
Acetonylacetone, 142 
Acetophenone, 149 
Acetylacetone, 104 
Acetylation test for alcohols, 152 
Acetylene, 184 . 
Acid anhydrides, 128, 80 
Acids, general characteristics, 37 
generic test for, 35 
losing carbon dioxide at 200°, 78 
neutralization equivalents of, 77 
tests for unsaturation in, 79 
titrations of, 35 
Aconitie acid, 49 
Acrolein, 23 
Adipic acid, 63 
Fsculin, 98 
Affinity constants, 36 
Alcohols, generic tests for, 151-154 
Aldehydes, general characteristics, 16 
as impurities in alcohols and ketones, 135 
generic test for, 15 
Alizarin, 211 
Bordeaux, 214 
yellow ‘‘ A”, 207 
yellow “C’’, 213 
cyanin “R’, 214 
Alkali, action on aldehydes, 16 
action on anhydrides and lactones, 128 
action on esters, 111, 117 
action on phenols, 87-88 
titrations with, 77 
Allyl alcohol, 167, 114 
Aluminium chloride, colorations with, 198 
Ammoniacal cuprous-chloride reagent, 199 
Ammoniacal silver-nitrate solution, 22 
Amy! acetate, 121 
Amyl alcohols, 114, 162 
Analytical procedure, the general, 1 


Anethol, 174 
Angelic acid, 53 
Aniline acetate paper, 33 
Anisic acid, 67 

aldehyde, 20 
Anisoin, 179 
Anisol, 189 
Anol, 94 
Anthracene, 200 
Anthraflavic acid, 213 
Anthraquinone, 216 
Apioh i174 
Apparatus, list of special, 237 
Arabinose, 30 
Arachidic acid, 55 
Arbutin, 97 
Asbestos-board screens, 10, 11, 81, 221 
Ash constituents, test for, 9 
Atropic acid, 58 
Aurine, 213 
Azelaic acid, 58 


B 


Barbaloin, 207 

Baths, covered, for heating tubes, 152 
ae for melting-point determinations, 

18 

Behenic acid, 56 

Beilstein’s Handbuch, references to, 7 

Benzaldehyde, 23 

Benzene, 200 

Benzhydrol, 157 

Benzil, 206 

Benzilic acid, 63 

Benzoic acid, 82 
anhydride, 53 

Benzoin, 139 

Benzophenone, 150 

Benzoquinone, 216 

Benzoylacetone, 92 

Benzyl alcohol, 165, 114, 167 

Boiling-point determination, 4, 221 
of small quantities by Siwoloboff’s Method, 

115, 222 

“‘Boiling-intervals,”’ 222 
table of, 227 

Borneol, 159 

Brassidie acid, 54 

Brazilin, 102 

Brazilein, 212 

Bradley’s color standard, 229 

“Broken” colors, 231 


239 


240 


Bromine, test for, 13 
test for unsaturation, 195 
water, in unsaturation tests, 195 
water, in testing phenols, 89 
Bumping, prevention of, 221 
Butyl alcohol, 168, 115 
Butyric acid, 81 


C 


Caffeic acid, 209 
Camphene, 175 
Camphor, 150 
Camphoric acid, 66 
Cantharidin, 129 
Capillaries, preparation of, 219 
Capric acid, 52 
Caproic acid, 75 
Caprylic acid, 76 
Carbohydrates, 26 
generic test for, 26 
generic characteristics, 27 
Carbon, tests for, 9 
dioxide, test for acids losing at 200°, 78 
tetrachloride, bromine solution in, 195 
Carnot’s procedure for identification of halo- 
gens, 13 
Carvacrol, 105 
Cellulose, 31 
Cerotic acid, 56 
Ceryl alcohol, 157 
Cetyl alcohol, 157 
Chelidoniec acid, 71 
Chemical purity, thermometric indications of, 
223 
Chlorine, test for, 14 
Cholesterine, 172 
Chromic-acid mixture for oxidations, 147 
Chrysarobin, 208 
Chrysene, 181 
Chrysophanic acid, 208 
Cinnamic acid, 82 
aldehyde, 21 
Cinnamyl] alcohol, 157 
Citraconic acid, 41 
Citral, 20 
Citric acid, 83 
Citronellal, 20 
Classification of compounds in this work, 1 
Ceerulein, 214 
Color, 230 
comparisons, 232 
standards, use of, 231 
symbols, table of, 232 
terminology, 230 
transitions, sharpness of, in titrations with 
indicators, 36 
Colored compounds of Order I, 204 
Confirmatory specific tests, 7 
Coniferine, 100 
Coniferyl alcohol, 93 
Constant boiling mixtures, 227 
Convolvulin, 98 
Cotoin, 207 
Coriandrol, 163 
Corrected boiling-points, 217, 222 
melting-points, 217 
Coumarin, 129 
Cresols, 91, 104 


ALPHABETICAL INDEX. 


Crotonic acid, 40, 74 
Cymene, 190 


D 


Daphnetin, 102 
Daphnin, 100 
Decinormal acid and alkali, 77 
Dehydracetic acid, 58 
Densities of water, table of, 229 
Dextrin, 29 
Dextrose, 30 
Diacetyl, 215 
Dibenzylidene acetone, 206 
Diethyl malonate, 123 
oxalate, 74 
succinate, 124 
succinylosuccinate, 96 
y-Diketones, pyrrol-red test for, 148 
Dimethyl oxalate, 40 
phthalates, 119, 126 
Diphenyl, 176 
methane, 174 
Diphenylene ketone, 207 
“Divisions,” defined, 1 
Drying precipitates, 235 
Dulcite, 156 
Durene, 176 


E 


Ebullator tubes, 223 
Elaidic acid, 54 
Empirical formula, use in identifications, 7 
Enols, 90 
Erucic acid, 53 
Erythrite, 155 
Esters, 111 
generic test for, 111 
“‘non-saponifiable,”’ 117 
saponification procedures for, 111, 113 
with characteristic odors, 79 
Ethers, saturated, test for, with sulphuric acid, 
199 
Ethyl acetate, 120 
acetoacetate, 104 
alcohol, 168 
benzene, 189 
benzoate, 123 
benzoylacetate, 106 
butyrate, 121 
cinnamate, 126 
ether, 160 
isobutyrate, 120 
isovalerianate, 121 
propionate, 120 
salicvlate, 105 


Ethylene, 184 


glycol, 169, 170 
oxide, 160 

Eucalyptol, 190 

Kugenol, 106 

Euxanthone, 210 

Examples illustrating the analytical proced- 
ure, 8 

Explosions in ignition tests, 10, 11 


F 


Fehling’s solution, 33 
Fenchone, 142 


ALPHABETICAL INDEX, 


Ferric chloride, colorations with, 107 
reagent, 87-88 
test for a-hydroxy-acids, 78 
Fisetin, 213 
Filtration in tests on a small scale, 235 
Flavopurpurin, 212 
Fluoresceine, 213 
paper, 14 
Fluorescence, observation of, 233 
Fluorene, 178 
Formic acid, 83 
Formic aldehyde, 114 
Fractionation tests for purity, 224 
Fructose, 30 
Fuchsine aldehyde reagent, 15 
“Full” colors, 228 
Fumaric acid, 72 
Furfurol, 24 
Furoin, 96 
Fusion interval, 224, 225 
Fusions with sodium, 10 


G 


Galactose, 30 
Galleine, 214 
Gallic acid, 70 
Galloflavin, 213 
Gallotannic acid, 50 
Gaseous compounds, classification of, 1 
Generic subdivisions, 6 
tests defined, 1 
tests, conclusiveness of, 7 
tests, tabular summary of, 5 
Genus, definition of, 1 
ieee eeiec 111,35; TV, 87; V, 111; VI, 
Poe tielse; VIL, 151: 1X, 173 
Genus, procedure for determining, 5 
Geraniol, 163 
Glucose, 30 
Glutaconic acid, 45 
Glutaric acid, 84 
Glycerine, 169 
Glycogen, 31 
Glycollic acid, 41 
Guiacol, 91 
Gum arabic, 29 


H . 


Hemateine, 214 

Hematoxylin, 207 

Halogens, tests for, when S and N are absent, 12 
tests for, when S and N are present, 13 
detection in presence of one another, 13 

Heptane, 182 

Hexane, 182 

Homogeneity, chemical, 3 
tests for, 3,223 

Hue of colors, 231 

Hydrocarbons, generic test for, 173 
sectional tests for, 173 

Hydrobenzoin, 158 

Hydrocinnamic acid, 54 

Hydrogen, test for, 9 

Hydroquinone, 108, 8 

a-Hydroxy-acids, tests for, 78 

Hydroxylamine reagent for ketones, 133 

Hypogeic acid, 52 


241 


I 


Ignition test for carbon, hydrogen, and ash, 9 
test with sodium for non-metallic elements, 


10 
tubes, 10 
Indene, 191 


Inosite, 156 
Inuline, 31 
Iodine solution, 166 
test for, 13 
Todoform test for alcohols, ete., 166 
Tron ignition tubes, 10 
Isoamyl acetate, 121 
alcohol, 162 
benzoate, 126 
butyratc, 122 
isovalerianate, 123 
Isobutyl acetate, 121 
alcohol, 114, 170 
benzoate, 125 
Isobutyric acid, 81 
aldehyde, 19 
Tsoprene, 184 
Isopropyl alcohol, 170, 114 
Isophthalic acid, 85 
Isopurpurin, 214 
Isovalerianic acid, 74 
aldehyde, 19 
Itaconic acid, 48 


K 
Ketones, generic tests for, 133, 134 
L 


Lactic acid, 39 
Lactide, 60 

Lactones, 128 
Lactose, 29 

Lauric acid, 53 
Levulinie acid, 39, 74 
Lovulose, 30 
Limonene, 190 
Linalool, 163 
Luminosity of colors, 230 
Luteolin 213 


M 


Maleic acid, 45 

Malic acid, 83 

Malonic acid, 45 

Maltose, 29 

Mandelic acid, 44 

Mannite, 155 

Margaric acid, 54 

Meconin, 58 

Melissic acid, 56 

Mellitie acid, 51 

Melting-point apparatus, 218, 225 
corrections, 217, 218, 220 
determination, 218-220 
determination in sealed capillaries, 219 
the true, of a compound, 220 

Menthol, 157 

Menthone, 143 

Mesaconic acid, 50 

Mesitylene, 200, 8 

Mesityl oxide, 141 





242 


Mesotartaric acid, 46 
Metallic salts, precipitations, 80 
“Method of the empirical formula,” 
Methyl acetate, 120 

alcohol, 171, 114 

benzoate, 120 

butyrate, 120 

formate, 120 

ethyl ketone, 141 

propyl ketone, 141 

propionate, 120 

salicylate, 105 
Methylal, 19 
Milk sugar, 29 
Mixtures, examination of, 4 
Molisch, test for carbohydrates, 26 
Mucic acid, 69, 34 
Myristic acid, 54 


ill, 7 


N 


Naphthalene, 201 

Naphthazarin, 214 

Naphthols, a and £, 108 

Naphthoic acid, 64, 66 

a-Naphthol, as reagent for Test II, 26 
a-Naphthoquinone, 216 

Neutralization equivalents, determination of, 

“eel 


equivalents, formula for calculating, 77 
Nitric acid, oxidations with, 198 
fuming, in sectional tests with the hydro- 
carbons, 196 
Nitrogen, tests for, 12 
Nitroprusside of sodium, solution, colorations 


with, 146 
Nitrosylsulphuric acid reagent, 13 
Nonane, 183 
Numbered specific, semi-specific, and sectional 
tests 2, 7 
O 
Octane, 183 


Octyl alcohol, 163 
Odors of esters in tests for acids, 79 
Oleic acid, 52 
Oenanthol, 20 
Oenanthylic acid, 76 
Opacity, 134 
Opianic acid, 63 
Orcin, 95 
Order, definition of, 1 
determination of, 4, 9 
Ordinal tests, definition, 1 
directions for, 9 
Orsellinic acid, 66 
Osazone precipitations, 32 
Oxalic acid, 84 
Oxidation, of carbohydrates, 34 
of side-chains, 197 
of alcohols, and ketones, 147 
with copper spiral, 171 
with chromic acid mixture, 147, 198 
with dilute nitric acid, 198 
with potassium permanganate, 197 
Oxybenzoic acids, 64, 68, 69 


Ee 


Palmitic acid, 54 
Paraconic acid, 40 


ALPHABETICAL INDEX. 


Paraffin, protection of corks by, 153 

Paraformaldehyde, 18 

Paraldehyde, 19 

Pelargonic acid, 76 

Pentane, 182 

Perseite, 156 

Peucedanin, 119 

Phenacetolin, 213 

Phenanthrene, 201 

Phenanthrenequinone, 216 

Phenetol, 190 

Phenol, 108, 114 

Phenols, generic tests for, 87 
properties and reactions of, 89 

Phenolphthalein, solution, 35 
behavior as indicator, 36 

Phenylacetic acid, 55 

Phenylhydrazine, as reagent, 16, 32, 134 
hydrochloride, preparation, 32 

Phloridzin, 99 

Phenylpropiolic acid, 62 

Phloroglucine, as reagent, 33 
test for, 109 

Phoron, 136 

Phosphorus, tests for, 12, 11 

Phthalein fusion, 107 

Phthalic acid, 84 

Phthalic anhydride, description of, 61 
use as reagent, 107 

Phthalid, 129 

Physical ‘properties, examination of, 4 

Phytosterin, 158 

Picene, 181 

Pycnometer, capillary, 228 

Picric acid, as reagent, 89 

Picrotoxine, 100 

Pimelic acid, 43 

Pinacone, 155 

Pinacoline, 141 

Pinene, 189 

Piperic acid, 210 

Piperonal, 17 

Piperonylie acid, 72 

Pipette, for specific gravities, 229 
safety, 236 

Polyatomic alcohols, acetylation of, 154 

Polymerized aldehydes, 15 

Potassium permanganate, 

197 
permanganate, 
79 


oxidations with, 
in tests for unsaturation, 


sulphate baths, 219 
Precipitates, filtration and drying of, 234 
Precipitation of metallic salts, 80 
Propionic acid, 81 

anhydride, 75 
Propyl alcohol, 115, 172 

acetate, 120 
Protocatechuic acid, 50 
Pseudocumene, 201 
Pulegone, 143 
Purity, chemical, evidences of, 3 

of a color, 230 
Purpurin, 210 
Pyrene, 179 
Pyrocatechin, 109 
Pyrogallol, 110 
Pyromucic acid, 45 
Pyrrol-red, 148 


ALPHABETICAL INDEX. 243 


Q 
Quercite, 156 
Quercetin, 213 
Quinic acid, 48 
Quinhydrone, 208 

R 


Racemic acid, 50 
Raffinose, 29 
Reagents, list of special, 236 
Resorcin, 110 
as reagent, 85, 171 
Retene, 177 
Rhamnose, 30 
Ricinoleic acid, 52 
Rosolie acid, 213 
Rufigallic acid, 214 


Ss 


Saccharic acid, from oxidations, 34 
Saccharose, 29 
Safety pipette, 53 
Safrol, 192 
Salicin, 100 
Salicylic acid, 85 
aldehyde, 20 
Saligenin, 93 
“Salting-out” effect-of alkali, 117 
Santalin, 206 
Santonin, 129 
Saponifications, methods, 111, 113 
equivalents, 112, 113 
products, neutral, 113 
products, acidic, 116 
Saturated colors, 230 
Schotten- Baumann reaction, 37 
Scoparin, 209 
Sebacic acid, 61 
Section, defined, 1 
Sectional tests, 2 
Semi-specific tests, 2 
Sesquiterpenes, 193 
Shades, of a hue, 231 
Sharpness, in end reactions, 36 
in boiling- or melting-points, 223, 226 
Side-chains, oxidation of, 197 
Silver nitrate, ammoniacal, 22 
salts of volatile fatty acids, 148, 149 
Siwoloboff’s boiling-point determination, 222 
Small preparations, manipulations in, 234 
Sodium, as reagent, 16, 151, 154 
bisulphite, as reagent, 16 
nitroprusside, as reagent, 146 
Solubility, approximate determination of, 38 
degrees of, 38 
Sorbic acid, 61 
Sorbinose, 30 
Sorbite, 155 
Species, chemical, 2 
chemical, identification of, 6 
Specific gravity, determination of, 227 


gravity, determination, for small quanti- 


ties of liquids, 228 
gravity, pipette, 229 
tests, definition of, 2 
Starch, 31 
Stearic acid, 55 
Stearolic acid, 53 
Stem-exposure corrections, 218, 222 


Stilbene, 178 
Styrene, 189 
Suberic acid, 62 
Sub-order II, 204 
Substitutions by bromine, 195 
Succinic acid, 86 
anhydride, 60 
Sulphur, tests for, 11, 12 
Sulphuric acid, as reagent in testing ethers 
and hydrocarbons, 200 
fuming, use in sectional test with hydro- 
carbons, 196 
Superheating, prevention in boiling-point deter 
minations, 221 
Supersaturation of solutions, 235 


4 


Tannic acid, 50 
Tartaric acid, 83 
Terephthalic acid, 85 
Terpineol, 165 
Thermometers, 219 
Thujone, 143 
Thymol, 110 
Thymoquinone, 205 
Tiglic acid, 40 
Tiles, porous for absorption, 235 
Tints, of a hue, 231 
Titration, of acids, 35 

of acid anhydrides, 37 
Tolane, 176 
Tollen’s ammoniacal silver reagent, 22 
Toluene, 202 
Toluic acid, 66 
Toluides, identification of fatty acids as, 81 
Toluidine, para, as reagent, 80 
Tricarballylic acid, 48 
Trimethyleneglycol, 165 
Triphenylmethane, 177 
Triple bonding, test for, 199 
Tropic acid, 61 
True melting-point, 219 
Truxillic acids, 70 


U 


Undecylenic acid, 52 

Unsaturated acids, tests for, 79 

Unsaturation, bromine test for, 195 
permanganate test for, 79 


V 
Valerianic acid, 74 

Vanilline, 17 

Vanillic acid, 69 

Veratric acid, 66 

Volatile fatty acids, identification of, 147 


W 


Water, table of densities for, 229 
of crystallization, removal of, 38 
Wave-length of standard colors, 232 


x 


Xanthone, 180 
Xanthopurpurin, 210 
Xylenes, 202 

Xylenols, 91, 92 

Xylidene acetate paper, 33 
Xylose, 30 


FORMULA INDEX. 


Tuer Formula Index gives the page, and usually the part of the page, on which any compound of known 
empirical formula described in this volume will be found. The numerals following a dash—which is commonly 
preceded by a melting-point or boiling-point—are the page numbers. The compounds are arranged accord- 
ing to the kind and number of atoms represented in their symbols. This form of index—already used in Richter’s 
Lexicon and many of the leading chemical journals—is so simple that detailed explanations are not necessary. 
Polymers and compounds cf unknown molecular weight are mentioned under the simp!est formula expressing 
their percentage composition. Water of crystallization is always omitted from the formule. To facilitate 
access to the original literature, the names applied to compounds are generally literal English translations of 
names used in the indexes of the third edition of Beilstein’s Handbuch der organischen Chemie. Incidentally 
it is possible to use this index in identifying compounds by the ‘‘Method of the Empirical Formula.” 


C, GROUP. Glycid, bp. 161°—164 
CH, Methane, bp. — 153°—182 Methyl acetate, bp. 57°—120 


CH,O Formalin, bp. 98°—19 Propionie ac., bp. 141°—73 
: Paratocne enn mp. abt. 120°— CHO, Dimethyl carbonate, bp. 91°—120 


18 aan ac., mp. mC: ? 
CH,O Formic ac., bp. 101°—73 Methoxyacetic ac., bp, 203°—74 
CHO Methyl alc., Gr 66°—160 Methyl glycollate, bp. 151°—121 
C;H,O Isopropyl alc., bp. 88°—161 
C, GROUP. tee aur bp. 11°—160 
ro . 97°— 
C,H, Acctylons bere ea melee C.H,O, Methyl Banas 2 
C.H, Ethylene, bp. — 103°—184 nae: Propylene glycol b 188°—164 
C,H, Ethane, bp. —86°—182 Trimethylene gl ete 214°—165 
( O,)x Polyglycollid, mp. 220°—130 C.H.O Glycerine, bp 390°. 165 
C,H.0, Oxalic av se es pet depas 
OHO Acetic ald., bp. 21°— 
ee Ethylene oxide, bp. 14°—160 C ta Ae 
Paraldehyde, bp. 124°—19 CHG Butadiénes, bp. 1° and 18°—184 
Metaldehyde, mp. 110°—18 Caoutchene, bp. 14°—184 
C,H,O, Acetic ac., bp. 118°—73 Ethylacetylene, bp. 18°—184 
Methyl formate, bp. 32°—73 Butine(2), bp. 28°—184 
C.H,O, Glycollic ac., mp. 78°—161 CA; Butenes, bp. 1° and 2°—184 
C,H,O Ethyl alc., bp. 78°—161 : Methyleyclopropane, bp. 4°—184 
Methyl eth., bp.—24°—160 CHyo Butane, bp. +1°—182 
as ane hy eae mp. 0°—182 
pi Fe Maleic anhyd., mp. 56°—54 
C; GRODE. C,H,0, AcotylonesieNt bene ac., mp. 178° 
Cash, Propylene, bp. — 50°—184 —49 
Cyclopropane, bp. —35°—184 C,H,O Furfurane, bp. 31°—189 
Cau, Propane, mp. —38°—182 ClO, Tetrolic ac., mp. 76°—40 
C,H:0 Propargyl ald., bp. 60°—19 C,H,0, Succinic anhyd., mp. 119.6°—60 
CaO: Propiolic ac., bp. 144°—73 C Ho Fumaric ac., sb. w. m. 200°—68 
C,H,O Acrolein, bp. 52°—19 Glycolid, mp. 86°—129 
Allylene oxide, bp. 62°—160 Glutinic ac., mp. 145° d—46 
Propargyl! alc., bp. 114°—164 Maleic ac., mp. 130°—45 
C,H,0, Acrylic ac., bp. 140°—73 Cro: Oxalacetic ac., mp. 172° d—48 
C.H,O, Pyruvic ac., bp..165°-—/4 C,H,0,  Dioxymaleic ac., d. abt. 155°—64 
C,H,0O, Malonic ac., mp. 132°—45 C,0,0 a-Crotonic ald, bp. 104-5°—19 
OA sit 6» Tartronic ac., mp. 186° (?)—49 Hydrofurfurane, bp. 67°—189 , 
CH OF Mesoxalic ac., mp. 119°—44 Methyl propargyl eth., bp. 61°— 
C,H,O Acetone, bp. 56.5°—141 160 
Ally] afc., bp. 97°—161 Vinyl eth., bp. 39°—160 
Metapropionic ald., mp. 180°—18 UT. Allyl formate, bp. 82.5°—i20 
Propionic ald., bp. 48.8° ¢.—19 Butenoic ac., bp. 168°—74 
Propylene oxides, bp. 35°, 50°—160 y-Butyrolactone, bp. 206°—~-131 
C.H,O,  Acetylearbinol, bp. 147°—142 Crotonic ac., mp, 72°—40 
Ethyl formate, bp. 54°—120 Diacetyl, bp 88°—2Z15 


244 


C,H,0; 
C,H,0, 


C,H,0, 


C,H,0, 


C,H,,0, 


CHO; 
C,H yO, 


C,H, 


FORMULA INDEX. 


Erythrite anhyd., bp. 1388°—164 
Isocrotonic ac., bp. 169°—74 
Methacryliec ac., bp. 162°—73 
Methyl acrylate, bp. 80.3°—120 
Trimethylenezaroonic ac., bp. 182° 
—74 
Acetic anhyd., bp. 137°—73 
Methyl pyruvate, bp. 135°—121 
Acetylperoxide, mp. 30°—52 
Dimethyl oxalate, mp. 54°—40 
Isosuccinic ac., mp. 1385°—45 
Succinic ac., mp. 1&85°—49 
Diglycollic ac., mp. 14S8°—47 
Glycollic anhyd., mp. 129°—61 
Isomalic ac., abt. 140°—46 
Malic acids, mp. 100°, 133°—43, 45 
Methyltartronic ac. mp., 178° d.—49 
Mesotartaric ac., mp. 142°—46 
Racemic ac., mp. 205°—50 
Tartaric ac., mp. 169°—48 
Dioxytartaric ac., mp. 115° d.—44 
Butyric ald., bp. 73-4°—19 
Crotyl alc., bp. 117°—161 
s-Dimethylethylene oxide, bp. 56° 
—160 
Isobutylene oxide, bp. 51°—160 
Isobutyric ald., bp. 63—4°—19 
Methy! allyl eth., bp. 46°—160 
Metyl ethyl ketone, bp. 81°—141 
Vinyl ethyl eth., bp. 35°—160 
n-Butyric ac., bp. 162°—73 
Dioxyethylene, bp. 102°—164 
Ethyl acetate, bp. 77°—120 
Isobutyric ac., bp. 155°—73 
Isopropyl formate, bp. 69°—120 
Methyl propionate, bp. 79.9°—120 
Propyl formate, bp. 81°—120 
Ethyl glycollate, bp. 160°—122 
Ethoxyacetic ac., bp. 206°—74 
Methyl ethyl carbonate, bp. 109°— 
120 
Methyl lactate, bp. 145°—73 
Methyl methoxyacetate, bp. 127.3° 
—121 
a-Oxybutyric ac., mp. 43°—39 
a-Oxyisobutyric ac., mp. 79°—41 
af-Dioxybutyric ac., mp. 74°—40 
Methylisoglyceric ac., mp. 74°—40 
Methylpropanedioic ac., mp. 100°— 
43 


Trioxyisobutyric ac., mp. 116°—44 
Butyl alc., bp. 117°—161 
sec.-Butyl alc., bp. 100°—161 
Isobutyl alc., bp. 106°—161 
Ethyl eth., bp. 35°-—160 
Methyl propyl eth., bp. 40°—160 
Trimethylearbinol, bp. 83°—161 
Butanediols, bp. 204°—164, 165 
Dihydroxybutane, bp. 183°—164 
Dihydroxymethylpropane, bp. 177° 
—164 
Dimethylacetal, bp. 64°—19 
Ethyleneglycol monoethy] eth., bp. 
135°—164 
Glycol dimethyl eth., bp. 83°—161 
Diethylene glycol, bp. 250°—165 
Erythrite, mp. 126°—155 


C, GROUP. 
Cyclopentadiéne, bp. 42°—185 


C,H, 


CsHi. 


C,H,0, 
CHO. 


C;H,O; 


C,H 2 


C5H.0s 
C.H,O, 


C.H,0, 
C.H,0, 
C,H,O 


C;H,05 


245 


Valylene, bp. 50°—185 
Pirylene, bp. 60°-—185 
Isopropylacetylene, bp. 28°—184 
Isoprene, bp. 36°—la4 
Methylbutadiéne, bp. 41°—184 
Piperylene, bp. 42°—1&5 
Cyclopentene, bp. 45°—185 
Propylacetylene, bp. 48°—185 
Valerylene, bp. 56°—185 
Dimethyleyclopropane, bp. 21°— 
184 
Isopropylethylene, bp. 21°—184 
Methylethylethylenes, bp. 31° 
and 36°—184 
Trimethylethylene, bp. 37°—184 
Propylethylene, bp. 39°—184 
Methyleyclobutane, bp. 40°—182 
Cyclopentane, bp. 50°—182 
2-Methylbutane, bp. 31°—182 
Pentane, bp. 37°—182 
Croconic ac.—213 
Coumalin, bp. 207°—131 
Furfurol, bp. 161°—20 
Citraconic anhyd., 0. 213°—76 
Glutaconic anhyd., mp. 87°—56 
Pyromeconic ac., mp. 117°—59 
Pyromucic ac., mp. 183°—45 
Ethyl propiolate, bp. 119°—121 
Furfuralcohol, bp. 169°—164 
Leevulinice anhydrides, bp. 167°, 
208°—131 
Pentinoic ac., mp. 102°—43 
Propargyl acetate, bp. 124°—121 
Glutaric anhyd., mp. 56°—54 
Tetrinic ac., mp. 189°—67 
Citraconic ac., mp. 80°—41 
Ethylenemalonic ac., mp. 140°—46 
Glutaconic ac., mp. 132°—45 
Itaconic ac., mp. 161° d.—48 
Mesaconic ac., mp. 202°—50 
Paraconic ac., mp. 57°—40 





Trimethylenedicarbonic ac., mp. 
175°—48 
Acetonedicarbonic ac., mp. 135° 
d.—45 
159° 


Ethenyltricarbonic ac., mp. 
7 


Acetyltrimethylene, bp. 114°—141 
Cyclopentanone, bp. 180°—141 
Ethylideneacetone, bp. 122°—141 
Ethyl propargyl] eth., bp. 80°—161 
Leevulinie ald., 187° d.—20 
Methylbutenon, bp. 100°—141 
Tetramethylene ald., bp. 116°—19 
Tiglic ald., bp. 116.6°—19 
Acetylpropionyl, bp. 108°—215 
Allyl acetate, bp. 103.5°—120 
Allylacetic ac., bp. 188°—75 
Angelic ac , mp. 45.5°—53 
Dimethylacrylic ac., mp. 70°—40 
Ethyl acrylate, bp. 98.5° c.—120 
a-Ethylacrylic ac., mp. 45°—39 
Methylbutyrolactone, bp. 204°— 
131 
Methyl crotonate, bp. 120.7°—121 
Methyltrimethylene carbonic ac., 
bp. 191°—74 
Pentenoic ac ds, bp. 194°, 200°—74 
Tetramethylenecarbonic ac., bp. 
195°—75 


246 


C;Hs03 


CHO; 


C.H,O, 


C;H,O, 
C,H,,0 


C,H,,0, 


C,H, 003 


FORMULA INDEX. 


Tiglic ac., mp. 64.5°—40 

y-Valerolactone, bp. 207°—131 

Itaconic anhyd., mp. 68°—55 

Levulinic ac., bp. 239°—74 

&-Methoxyisocrotonic ac., mp. 128° 
—61 

Acetoxylpropionic ac., mp. 166°— 
48 


Dimethylmalonic ac., mp. 192° d.— 
50 

Ethylmalonic ac., mp. 111°—43 . 

Glutaric ac., mp. 97.5°—42 

a-Hydroxylevulinic ac., mp. 103° 
—43 

Methyl ethyl oxalate, bp. 174°— 
122 

Methyl malonate, bp. 181°-—122 

Pyrotartaric ac., mp. 112°—43 

Citramalic acids, mp. 95°, 119°— 
42, 44 

Ethyltartronic ac., mp. 115°—44 

Methylmalic ac., mp. 123°—44 

6-Oxyglutaric ac., mp. 95°—42 

Trioxyglutaric acids, mp. 128°, 
152°, 154°—45, 47 

Diethyl ket., bp. 105°—141 

Kthylallyl eth., bp. 66°—160 

a-Ethylallyl ac., bp. 134°—162 

Ethyl isopropenyl eth., bp. 62°— 
160 


Tsovalerianic ald., bp. 92.5°—19 

Methylallylearbinol, bp. 115°—161 

Methyl isocrotyl eth., bp. 72°—185 

Methyl isopropyl ket., bp. 95°— 
141 


Methyl propyl ket., bp. 102°—141 

1, 4-Oxypentane, bp. 78°—161 

Pentamethylene oxide, bp. 81°— 
161 

Trimethylacetic ald., bp. 74.5°—19 

Valerianic ald., bp. 103°—19 

Vinylethylcearbinol, bp. 114°—161 

Acetylearbinolethylether, bp. 128° 

141 


Acetylpropyl alc., bp. 208°—143 
tert.-Butylcarbinol, mp. 52°—155 
Butyl formate, bp. 107°—120 
Ethyl propionate, bp. 98°—120 
Hydracetylacetone, bp. 176°—142 
Isobutyl formate, bp. 98°—120 
Isopropyl acetate, bp. 91°—120 
Isovalerianic ac., bp. 176° ¢.—74 
Methyl butyrate, bp. 102.3°—120 
Methylethylacetic ac., bp. 177°—74 
Methyl isobutyrate, bp. 92.38°—120 
Propyl acetate, bp. 102°—120 
Trimethylacetic ac., mp. 35°—39 
n-Valerianic ac., bp. 187°—74 
Diethyl carbonate, bp. 126°—121 
Methyl ethoxyacetate, bp. 145°— 
121 
a-Ethoxypropionic ac., bp. 196°— 
74 


Ethyl lactate, bp. 154°—73 

Ethyl methoxyacetate, bp. 131°— 
121 

Methyloxybutyric ac., mp. 67°—40 

Oxyvalerianic acids, mp. 31°, 85°— 
39, 41 

Propyl glycollate, bp. 170°—122 


C,H, 0% 
C.H,,.0; 


CH, 0, 
C5Hi205 


C,H,,0 


CoH, 


CoH, 


C,.H,0, 
CHO, 


Angliceric ac., mp. 110°—43 

Tigliceric ac., mp. 88°—41 

Arabinose, mp. 160°—30 

Xylose, mp. abt. 150°—30 

Arabonic ac., mp. 89°—41 

act. Amyl alc., bp. 129°—162 

n-Amyl alc., bp. 138°—162 

Diethylearbinol, bp. 116°—161 

Dimethylethylcarbinol, bp. 102°— 
161 

Ethyl propyl eth.. bp. 64°—160 

Isoamyl alc., bp. 180°—162 

Methylbutylearbinol, bp. 136°—162 

Methyl] butyl eth., bp. 70°—185 

Methylisopropylearbinol, bp. 112° 
—161 

Ethyl isopropyl eth., bp. 54°—160 

Methylpropylearbinol, bp. 118°— 
161 

Trimethyleneglycol ethyl eth., bp. 
160°—164 

Dihydroxypentanes, bp. 187°, 221° 
—164, 165 

Methylene diethyl ether, bp. §9°— 
19 


Ethyl glyceryl eth., bp. 227°-—165 
Pentaerythrite, mp. 253°—156 
Arabite, mp. 102°—155 


C, GROUP. 


Benzene, bp. 80°—189 
Hexadiéne, bp. 86°—186 
Diallylene, bp. 70°—185 
Hexadiéne, bp. 80°—185 
1, 2-Dihydrobenzene, bp. 83°—185 
1, 4-Dihydrobenzene, bp. 85°—185 
Dimethylbutine, bp. 38°—184 
Diallyl, bp. 59°—185 
Butylacetylene, bp. 70°—185 
Methylpentadienes, bp. 70° and 
77°—185 
Methylcyclopentenes, bp. 70° and 
72°—185 
Methylpentine, bp. 72°—185 
Ethyldivinyl, bp. 73°—185 
Hexadiéne (1, 3), bp. 73°—185 
Methylpropylacetylene, bp. 83°— 
1 


85 

Dimethylethylethylene, bp. 66°— 
185 

s-Methylpropylethylene, bp. 68°— 
185 


Butylethylene, bp. 69°—185 
Methylethylpropylene, bp. 70°— 
185 


Methylcyclopentane, bp. 71°—182 

Tetramethylethylene, bp. 73°—185 

Cyclohexane, bp. 81°—182 

Trimethylethylmethane, bp. 50°— 
182 

Diisopropyl, bp. 58—182 

2-Methylpentane, bp. 62°—182 

Methyldiethylmethane, bp. 64°— 
182 

Hexane, bp. 69°—182 

Diacetylenedicarbonic ac, 
177°—49 

Benzoquinone, mp. 116°—206 


mp. 


Gs ROP 
C,H,0; 


CsHe6O 
C,H,O, 
C,H,O, 


CoH,O3 


C.H,O, 
C.H,O, 
C.H,Os 
C,H,O 

C,H;0, 


C,H;0; 


C.H3:0, 


C.H,.02 


FORMULA INDEX. 


Coumalic ac., mp. 207° d.—69 
Comanic ac., mp. 250°—71 
Comenic ac., d. 260°—71 
Furfuranedicarbonic ac., 
(2 
Phenol, mp. 42°—91 
Hydroquinone, mp. 169°—99 
Methylfurfurol, bp. 187°—20 
Pyrocatechin, mp. 104°—94 
Resorecin, mp. 116°—95 
Betulin, mp. 258°—159 
Maltol, mp. 159°—98 


sbl. w. 


Methylpyromucic ac., mp. 108°—59 


Oxyhydroquinone, mp. 140.5°—97 
Phenoglucin, mp. 200.5°—100 
Phloroglucine, mp. 217—9°—101 
Pyrogallol, mp. 133°—96 
Dimethyl acetylenedicarbonate, bp. 
196°—123 
Muconic ac., d. abt. 320°—72 
Aconitic ac., mp. 191° d.—49 
Trimethylenetricarbonic acids, mp. 
151°, 184° c., 220°—47, 49, 51 
s-Ethanetetracarbonic ac., mp. 
170°—48 
Dimethylfurfurane, bp. 93°—189 
Hexinone, bp. 149°—142 
Dihydroresorcin, mp. 105°—94 


Propylacetylenecarbonic ac., mp. 
at 39 

Sorbic ac., mp. 134°—61 

s-Dimethylsuccinic anhyd., mp. 
87°—56 

Ethylsuccinylosuccinic ac., mp. 


128°—96 
Allylmalonic ac., mp. 103°—43 
Dimethyl fumarate, mp. 102°—119 
Dimethyl maleate, bp. 205°—123 
Ethylfumaric ac., mp. 194°—67 
Monoethyl fumarate, mp. 70°—55 
Ethylmaleic ac’, mp. 100°—43 
Hexenedioic ac., mp. 195°—67 
Lactide, mp. 128°—60 
Methyleyclopropanedicarbonic ac., 
mp. 113°—43 
Methylglutaconic ac., mp. 137°—46 
Methylitaconic ac., mp. 166°—48 
Tetramethylenedicarbonic acids, 
Beals too, 138°, 157°, 170°— 
45, 46, 47, 48 
Ethyl oxalylacetate, mp. 96°—94 
Glucuronic anhyd., mp. 176°—49 
Tricarballylic ac., mp. 166°—48 
Citric ac., mp. 153°—47 
Allylacetone, bp. 128°—141 
Allyl eth., bp. 94°—161 
Cyclohexanone, bp. 155°—142 
Mesityl oxide, bp. 129.5°—141 
Methylethylacrolein, bp. 137—19 
Methylcyclopentanone, bp. 142°— 
142 
Methyl tetramethylene ket., bp. 
135°—142 
Acetonylacetone, bp. 194°—142 
Acetylisobutyryls, bp. 115°, 128°— 
215 
y-Caprolactone, bp. 220°—131 
Dimethylbutenoic ac., mp. 70°—40 
Ethyl a-crotonate, bp. 142°—121 





CoH,.O; 


CoH,0, 


(C,H,,O0;)% 


C.H,.0¢ 


CoH O08 


C,H,,0 


247 


a-Ethylerotonic ac., mp. 41°—53 

Ethyl isocrotonate, bp. 136°—121 

Ethyl methacrylate, bp. 117°-—121 

Hexenoic acids, mp. 33°, bp. 206° 
203°—53, 75 , 

Isocaprolactone, bp. 207°—131 

Methylpentenoic acids, mp. 24°; 
bp. 211°, 213°—52, 76 

Methylvalerolactone, bp. 206°— 
131 

Pentamethylenecarbonic ac., bp. 
214°—76 

Propionylpropionic ald., mp. 40°— 
17 


y-Acetylbutyric ac., bp. 275°—74 
$-Ethoxycrotonic ac., mp. 137°—62 
Ethyl isoacetoacetate, bp. 128.5°— 


121 
Ethyl methylformylacetate, bp. 
161°—20 
Glycerine eth., bp. 171°—164 
Propionic anhyd., bp. 169°—75 
£-Propionylpropionic ac., mp, 32°— 
39 


Adipic ac., mp. 153° c.—63 
Diethyl oxalate, bp. 186°—74 
Dimethylsuccinic acids, mp. 129°, 
139°, 195°, 209°—45, 46, 67, 50 
Ethoxylsuccinic ac., mp. 86°—41 
Ethylsuccinie ac., mp. 98°—42 
Jsomannide, mp. 87°—155 
Isopropylmalonic ac., mp. 87°—41 
Methylethylmalonic ac., mp. 118°— 
44 
a-Methylglutaric ac., mp. 77°—41 
Methyl isosuccinate, bp. 179°—122 
3-Methylpentanedioic ac., mp. 85° 
—41 


Methyl succinate, bp. 195°—123 
Propylmalonic ac., mp. 96°—42 
Cellulose—31 
Dimethylmalic ac., mp. 130°—45 
Ethoxysuccinic ac., mp. 78°—41 
Glycogen, mp. abt. 240°—31 
Lactic anhyd., mp. 255°—71 
a-Oxyadipic ac., mp. 151°—47 
Saccharin, mp. 160°—129 
Starch—31 
Dimethyl racemate, mp. 85°—119 
Dimethyl tartrate, mp. 48°—118 
Monoethyl tartrate, mp. 90°—42 
Isosaccharic ac., mp. 185°—49 
Mucic ac., mp. 206° d.—69 
Saccharic ac.—34_ 
Talomucic ac., mp. 158° d.—47 
Caproic ald., bp. 129°—19 
Cyclohexanol, bp. 160°—163 
Dimethylallylearbinol, bp. 119°— 
162 
Ethyl isocrotyl eth., bp. 93°—186 
Ethyl isopropyl ket., bp. 114°— 
141 


Ethyl propyl ket., bp. 123°—141 
Hexenyl alc, bp. 187°—162 
Methyl] butyl ket., bp. 127°—141 
Minho bp. 138°— 


Methylethylacetone, bp. 118°— 
141 


248 


C.H,,0, 


C.H,.0; 


C,.H,,0, 
C.H,,0; 
C.H,,0. 


C,H,,0 


C,H,,0, 


FORMULA INDEX. 


Methyl] isobutyl ket., bp. 116°— 
141 


1, 5-Oxyhexane, bp. 106°—161 
Pinacoline, bp. 106°—141 
Amyl formate, bp. 130°—121 
Butyl acetate, bp. 125°—121 
Caproic acids, bp. 197°, 206°—75 
Diacetone alc., bp. 164°—142 
Diethylacetic ac., bp. 190°—74 
Dimethylethylacetic ac., bp. 187°— 
75 


Ethyl butyrate, bp. 120°—121 

Ethyl isobutyrate, bp. 110°—120 

Isobutyl acetate, bp. 116°—121 

Isobutylacetic ac., bp. 208°—75 

Isoamyl formate, bp. 123°—121 

Methylpropylacetic acids, bp. 
190°, 193°—75, 74 

Methyl] isovalerianate, bp. 127°— 
121 

Methyl trimethylacetate, bp. 
101°—120 

Methyl valerianate, bp. 127°— 
121 

Allyl glyceryl eth., bp. 240°—165 

Cyclohexantriol, mp. 184°—156 

Ethoxyisobutyric acids, bp. 181°, 
217°—75, 74 

Ethyl ethoxyacetate, bp. 152°— 
121 


Ethyl oxyisobutyrate, bp. 150° 

—121 

Ethyl a-oxybutyrate, bp. 165°— 
122 

Methylpentanoloic ac., mp. 73°—40 

a-Oxycaproic ac., mp., 61°—40 

Oxydiethylacetic ac., mp. 80°—41 

Paraldehyde, bp. 124°—19 

Ethyl dioxybutyrate, bp. 227°— 
124 

Quercite, mp. abt. 230°—156 

Rhamnose, (isodulcite)—30 

Fructose (Levulose), mp. 94°—30 

Galactose, mp. 168°—30 

Glucose, mp. 146°—30 

Inosite, mp. 225° c.—156 

Mannose,—29 

Sorbinose mp. 164°—30 

Dimethylisopropylcarbinol, bp. 118° 
—16l 


Ethylisopropylearbinol, bp. 128°— 
162 


Ethyl butyl eth.. bp. 92°—186 

Ethyl! isobutyl eth., bp. 79°—185 

Ethylpropylearbinol, bp. 1385°— 
162 


act.-Hexyl alc.. bp 154°—162 

Hexyl ale. bp 157°—163 

Isopropyl eth.. bp 69°—160 

Isohexylearbinol, bp. 150°—162 

Methyldiethylearbinol, bp. 123°— 
162 

Methylisobutylearbinol, bp. 130°— 
162 


Methylpropylearbincarbinol, bp. 
147°—162 

Pinacoline ale . bp. 120°—162 

Propyl ether, bp. 91°—161 

Acetal, bp 104°—19 

Dihydroxyhexane, bp. 206°—165 


BA Sly 4 
C,H,,0. 
C,H,,0 


Glycol diethyleth., bp. 123°—162 

Pinacone, mp. 36°—155 

Triethylene glycol, bp. 290°—165 

Rhamnite, mp. 121°—155 

Mannite, mp. 163°, 166°, 168°— 
155, 156 

Dulcite, mp. 188°—156 

Sorbite, mp. 110°—155 

Pinacone hydrate, mp. 56°—155 


C, GROUP. 


Toluene, bp. 111°—189 
Tropilidene, bp. 114°—189 
Dihydrotoluene, bp. 107°—186 
Heptone, bp. 115°—1&6 
Cycloheptadiéne, bp. 120°—189 
Ethylpentadiéne, bp. 97°—186 
(inanthylidene, bp 102°—186 
Heptine, bp. 103°—1&6 
Ethylpropylacetylene, bp. 105°~ 
186 


Toluenetetrahydride, bp. 105°— 
186 


Methylbutylacetylene, bp. 112°~ 
186 


Cycloheptene, bp. 114°—1&6 
Dimethylpentene, bp. 77°—185 
Trimethylbutene bp. 79°—185 
Dimethylpentene, bp. £3°—185 
Dimethylcyclopentane, bp. 94°-— - 
182 
Ethylpentene, bp. 97°—1&6 
Heptene(1), bp. 98°—1&6 
Hexahydrotoluene, bp. 101°—182 
Cycloheptane, bp 118°—182 
Dimethyldiethylmethane, bp. 86°— 
182 
Methylhexanes, bp. 90° and 91°— 
182 
Triethylmethane, bp. 96°—182 
Heptane, bp. 98°—182 
Chelidonic ac., mp. 262°—71 
Benzaldehyde, bp. 179.5°—20 
Benzoic ac., mp. 121.2° e.—60 
Furfuracrolein, mp. 51°—17 
Oxybenzaldehydes, mp. 
115°—17, 18 
Salicylic ald., bp. 196.5°—20 
Toluquinone, mp. 68°—205 
Furfuracrylic ac., mp. 141°—62 
m-Oxybenzoic ac., mp. 200°—68 
p-Oxybenzoic ac., mp. 210°—69 
Salicylic ac., mp. 158° e.—64 
Dioxybenzoic acids, mp. 199°, 
204°, 205°, 232°—50, 50, 69, 51 
Protocatechuic ac., mp. 199° d.— 


Gallic ac., mp. abt. 230°—70 
Pyrogallocarbonic ac., mp. 197° d. 
=n 


104°, 


Trimethylenetetracarbonic ac., mp. 
abt. 97°—42 

Anisol, bp. 155°—189 

Benzyl ale., bp. 205°—165 

p-Cresol, mp. 36°—91 

o-Cresol, mp. 30°—9i 

m-Cresol, bp. 203°—104 

Dibydrpben at aa bp. 170° d 
ae 


o_ 


C;H,0, 


C,H,O; 
C,H,0, 
C,H.0, 
C,H,,0 
C,H,,0; 
C,H, 0, 


C,H,.Os 


qe 10.6 


C,H,,0 


C,H,,0, 


C,H,,0, 


C,H,,0, 


FORMULA INDEX. 


Guiacol, mp. 31°—91 
m-Oxybenzyl ale., mp. 67°-—93 
Dioxytoluenes, mp. 64°, 103°, 124° 
—92, 94, 96 
Homopyrocatechin, mp. 51°—92 
Hydroquinone methyl eth., mp. 
53°-—-92 
Isohomopyrocatechin, mp. 47°—92 
Orcin, mp. 107°—95 
p-Oxybenzyl alc., mp. 110°—95 
Saligenin, mp. 86°—93 
Ethyl pyromucate, mp. 34°—118 
Methylpyrogallol, mp. 129°—96 
Uvic ac., mp. 135°—62 
Dicarboxyglutaric ac., mp. 167° 
d.—48 
Tretol, mp. 186°—100 
Cinchoic ac., mp. 168°—65 
Tetrahydrobenzaldehyde, bp. 187° 
Ethyl tetrinate, mp. 30°—118 
Diacetylacetone, mp. 49°—92 
Dimethyl citraconate, bp. 210°— 
123 
Dimethy] mesaconate, bp. 206°— 
123 
Dimeth yltrimethylenedicarbonic 
acids, mp. 176°, 213°—49, 50 
Ethylitaconic ac., mp. 164°—65 
Ethylmesaconic ac., mp. 172°—65 
Dimethyl itaconate bp. 211°—123 
Pentamethylenedicarbonic acids, 
mp. 88°, 140°, 159°—41, 46, 64 
Teraconic ac., mp. 162° d.—48 
Terebic ac., mp. 174°—66 
Hydrochelidonic ac., mp. 142°—62 
Dicarboxylpentanoic ac., mp. 141° 
d.—46 
Diallylearbinol, bp. 151°—162 
Methylcyclohexanone, bp. 169°— 
142 ; 
Propionyleyclobutane, bp. 155°— 
142 
Suberone, bp. 180°—142 
Acetylisovaleryl—215 
Allyl butyrate, bp. 142°—121 
Allyl isobutyrate, bp. 133°—121 
Ethyl allylacetate, bp. 143°—121 
Ethyl angelate, bp. 141°—121 
Ethyl tetramethylene carbonate, 
bp. 161°—122 
Ethy] tiglate, bp. 156°—122 
Ethylvalerolactone, bp. 219°—131 
Heptenoic ac., bp. 227°—76 
Hexahydrobenzoic ac., mp. 30°—52 
y-Ginantholactone, bp. 235°—131 
Teracrylic ac., bp. 218°—76 
Acetylvalerianic ac., mp. 41°—39 
Ethyl levulinate, bp. 205°—123 
Ethyl @-methoxyisocrotonate, bp. 
178°—122 
Mesitonic ac., mp. 74°—40 
Butylmalonic acids, mp. 76°, 101° 
—40, 43 
Diethyl malonate, bp. 198°—123 
Diethylmalonic ac., mp. 121°—44 
Dimethyl dimethylmalonate, bp. 
178°—122 
s-Dimethylglutaric 
128°, 140°—44, 46 


acids, mp. 


C,H,,0; 
C,H,,0.¢ 


C,H,,0 


C,H,,0, 


C,H1,0, 


249 


Dimethylpentanedioic acids, mp, 
84°, 100°—41, 42 

Ethyl acetoxylpropionate, bp. 178° 
—122 


Tsobutylmalonic ac., mp. 107°—43 
Isopropylsuccinic ac., mp. 117°— 
Sh 


Methylcarboxylpentanoic ac., nip. 
103°—43 

Methyladipic ac., mp. 94°—42 

Methylethylsuccinic acids, mp. 101°, 
169°, 180°—43, 65, 49 

Methyl ethyl succinate, bp. 208°— 
123 

Methylpropylmalonic 
106°, 121°—43, 44 

Pimelic ac., mp. 105°—43 

Propylsuccinic ac., mp. 91°—42 

Trimethylsuccinic ac., mp. 152°— 
47 

Diethyl tartronate, bp. 223°—124 

s-Methylethylmalic ac., mp. 132°— 
45 


acids, mp. 


Diethyl mesoxalate, mp. 57°— 
118 

Quinic ac., mp. 162° c.—48 

Diisopropyl ket., bp. 124°—141 

Dimethylpentanones, bp. 182°, 
137°, 126°—144, 142, 141 

Dipropyl ket., bp. 144°—142 

Ethyl isobutyl ket., bp. 136°—142 

Ethylpentanone, bp. 138°—142 

Ethyl valeryl eth., bp. 112°—186 

Methyl amyl ketones, bp. 144°, 
151°—142 

(nanthic ald., bp. 155°-—20 

Polycenanthylic ald., mp. 52°—17 

Suberyl alc., bp. 184°—164 

Amy] acetates, bp. 139°, 148°—121 

Amylacetic ac., bp. 221°—76 

Ethyl isovalerianate, bp. 134°—121 

Ethyl methylethylacetate, bp. 134° 
—121 

Ethylpropylacetic ac., bp. 209°—75 

Ethyl trimethylacetate, bp. 118°— 
121 

Ethyl valerianate, bp. 144°—121 

Isoamylacetic ac., bp. 209°—75 

Methyldiethylacetic ac., bp. 207°— 
75 


Methyl caproate, bp. 150°—121 
2-Methylhexanoic(1) ac., bp. 210°— 
5 


7 

Methyl isobutylacetate, bp. 150°— 
121 

Hexyl formate, bp. 154°—121 

(&nanthylic ac., bp. 223°—76 

Dipropyl carbonate, bp. 168°—122 

Ethyl a-ethoxypropionate, bp. 155° 
—121 

Ethyl a-oxyisovalerianate, bp. 175° 
—122 

Ethyl a-oxyvalerianate, bp. 190° 
—122 

2-Methylhexanoloic ac., mp. 64.5° 
—40 

Methyl oxydiethylacetate, bp. 165° 

122 


Oxycenanthylic ac., mp. abt. 60°— 
54 


250 


C,H,,0, 


CsHyi¢ 


CsHis 
C;H,0, 


C,H,0, 
C;H,O, 


CHO, 


FORMULA INDEX, 


Galactosecarbonic ac., mp. 145°— 


47 
Mannoheptonic ac., mp. 175° d.— 
49 C,H,O; 
Diisopropylearbinol, bp. 140°—162 
Dimethylisobutylearbinol, bp. 130° 
—162 
Dipropylearbinol, bp. 154°—162 
Ethyl isoamyl eth., bp. 112°— 
186 


C.H,O, 


Ethyl isobutylearbinol, bp. 147°— | C,;H,;O 
162 

Heptyl alc., bp. 176°—163 

Propyl butyl eth., bp. 117°—186 

Methylamylearbinol, bp. 164°—163 

Methylethylpropylearbinol, bp. 140° 
—162 

Methylisoamylearbinol, bp. 149°—. 
162 

Trimethylbutanol, bp. 131°—162 

Triethylearbinol, bp. 141°—162 

Trimethylene glycoldiethyl eth., 
bp. 140°—187 

Rhamnohexite, mp. 173°—156 

Perseite, mp. 188° c., 203° c.—156 


C, GROUP. 


Phenylacetylene, bp. 142°—189 
Styrene, bp. 146°—189 
Ethylbenzene, bp. 186°—189 
n-Xylene, bp. 138°—189 
m-Xylene, bp. 139°—189 
o-Xylene, bp. 142°—189 
m-Dihydroxylene, bp. 133°—187 
o-Dihydroxylene, bp. 134°—187 
Octone, bp. 134°—187 
p-Dihydroxylene, bp. 135°—187 
Trimethyleyclopentene, bp. 108°— 
186 
Dimethylhexadiéne, bp. 113°, 133° 
—186, 187 
2-Methylheptadiéne, bp. 117°—186 
Octadiéne, bp. 118°—186 
Ethylhexadiéne, bp. 122°—186 
Octine(1), bp. 131°—186 
Octine(2), bp. 183°—187 
Diisobutylene, bp. 102°—186 
s-Dimethyldiethylethylene, bp. 115° 
—186 
s-Diisopropylethylene, bp. 117°— 
186 


C,H,O, 


CsH,O3 


Hexahydroxylenes, bp. 118° and 
120°—182 
Methylethylcyclopentane, bp. 124° 
—183 
Octene(1), bp. 125°—186 
Dimethylhexane, bp. 108°—182 
Octane, bp. 125°—183 
Phthalic anhyd., mp. 128°—61 
Phthalid, mp. 73°—129 
Aldehydobenzoic acids, mp. 97°, 
165°, 285°—17, 18 
Benzoylformic ac., mp. 65°—40 
Piperonal, mp. 37°—17 
Aldehydosalicylic acids, mp. 179°, 
234°, 243°, 248° 18 
Isophthalic ac., mp. a.300°—72 
o-Oxyphenylglycollic ac., mp. 48°— 
39 


Cs;H,O, 


C,H,0; 


C;H,Os ’ 


Phthalic ac., mp. 184° d.—67 
Piperonylic ac., mp. 228°—70° 
Terephthalic ac., sbl. w. m.—72 
Furalmalonic ac., mp. 205° d.—69 
Oxyisophthalic acids, mp. 248°, 
388° c., 305°—70, 72 
Oxyphthalic ac., mp. 181° d.—49 
a-Resodicarbonic ac., mp, 276°—71 
Tetrahydroxyterepthalic ac., mp. 
139°—46 
Acetophenone, bp. 202°—142 
Phenylacetic ald., bp. 193°—20 
m-Toluic aldehydes, bp. 199°, 200° 
Anisic ald., bp. 248°—21 
Dimethylquinones, mp. 55°, 72°— 
205 
Furfuralacetone, mp. 39°—136 
Methyl benzoate, bp. 199°—123 
Methylenedihydrobenzoic ac., mp, 
33°—53 
Methoxybenzoic ald., mp. 35°—17 
Oxyacetophenone, mp. 86°—138 
Oxybenzoicaldehydemethyilether, 
bp. 230°—20 
Oxytoluic aldehydes, mp. 54°, 56°, 
110°, 115°, 172°, 209°—17, 18, 
65, 20 | 
Phenyl] acetate, bp. 196°—123 
Phenylacetic ac., mp. 76°—55 
Phloron, mp. 125°—206 
Toluic acids, mp. 102°, 110°, 176° 
—58, 59, 66 
Anisic ac., mp. 184.2° C.—67 
Diphenyl p-oxybenzoate, mp. 131° 
—119 


Mandelic ac., mp. 118°—44 
m-Methoxybenzoic ac., mp. 106°— 


58 

Methylethersalicylic ac., mp. 98.5° 
—d57 

Methylphenolcarbonic ac., mp. 183° 
—66 


Methylphenolmethanoic ac., mp. 
168°—65 
Oxyphenylacetic acids, mp. 129°, 
137°, 148°—45, 46, 47 
o-Oxymethylbenzoic ac., mp. 120° 
—60 
Oxyxyloquinone, mp, 103°—206 
Oxytoluic acids, mp. 151°, 163°, 
172°, 177°, 183°, 20670702 
63, 65, 66, 49, 69, 50 
Phenoxyacetic ac., mp. 96°—42 
Piperonyl ale., mp. 51°—157 
Quinacetophenone, mp. 202°—209 
Resacetophenone, mp. 142°—97 
Vanilline, mp. 80°—17 
Dehydracetic ac., mp. 108.5°—58 
Dihydrophthalic ac., mp. 215°—70 
Gallacetophenone (alizarin yellow 
C), mp. 168°-—99; 253 
Homogentisic ac., mp. 147°-—47 
Isodehydracetic ac., mp. 155°—64 
Methoxysalicylic ac., mp. 154°—63 
Orsellinic ac., mp. 176° d.—66 
Vanillic ac., mp. 207°—69 
Carbopyrotritaric ac., mp. 230°—70 
Methyl gallate, mp. 192°—119 


C,;H;O; 
C,H,,O 


CsH 0, 


CgH yO; 


Cs Hy O, 


CsHio O 6 
CsH Os 


CsH,,05 
CsH,,0, 


CsH,,05 


CsH,,0, 


CsH,,0; 
C;H,,0 


FORMULA INDEX. 


Methylfurfurancarbonacetic 
mp. 204°—68 

Tetramethylenetetracarbonic 
mp. 200° d.—50 

Benzvlearbinol, bp. 212°—165 

Cresyl methyl ethers, bp. 171°, 
175°—190 

p-Ethylphenol, mp. 46°—92 

Methyl benzyl] eth., bp. 167°—190 

Methylphenylearbinol, bp. 203°— 
164 

Phenetol, bp. 172°—190 

Tolylearbinols, mp. 34°, 59°, 217°— 
157, 165 

Xylenols, mp. 26°, 49°, 65°, 66°, 
74°, 75°—91, 92, 93 

Anisic ale., mp. 45°—157 

B-Orcin, mp. 163°—98 

Diethyl hydroquinolyl eth., mp. 
§5°—175 

Dimethyl resorcinyl eth., bp. 214° 
—192 

Dioxyxylol, mp. 120°, 149°—95, 97 

Homosaligenin, mp. 105°—94. 

Hydroquinone, ethyl eth., mp. 66° 

3 


ac., 


AC., 


Phthalic alc., mp. 64°—155 
Pyrocatechin, mp. 104°—94 
Saligenin methyl eth., bp. 247°— 
165 
Styrolene alc., bp. 205°—192 
Tolylene alc., mp. 112°, 46°—155 
Veratrol, bp. 205°—192 
m-Xylorcin, mp. 125°—96 
Methyluvinic ac., mp. 98°—57 
Pyrogalloldimethylether, mp. 51°— 
92 


Pyrogallol ethyl eth., mp. 95°—94 

Vanillyl alc., mp. 115°—95 

Biphenyldiolcarbonic ac., mp. 270° 
71 


Diallyl oxalate, bp. 216°—124 
Dimethylapionol, mp. 105°—95 
Oxalyldiacetone, mp. 120°—95 
Tetrahydrophthalic acids, mp. 
120°, 215°—44, 69 
Diacetylsuccinic ac., mp. d. 160°— 


Dicarboxyl-hexanedioic 
189°, 236°—49, 51 
Diethylacetic anhyd., bp. 230°—76 

Diallylacetic ac., bp. 227°—76 
Ethyl sorbate, bp. 195°—123 
Diallyloxalic ac., mp. 48°—53 
s-Diethylsuccinic anhyd., bp. 245° 


Ac. emp, 


ethyleneacetoacetate, bp. 


Ethyl diacetoacetate, bp. 202°—75 

Diethyl fumarate, bp. 218°—124 

Diethyl maleate, bp. 225°—124 

Hexahydrophthalic acids, mp. 
192°, 215°—67, 69 

Terpenylic ac., mp. 90°—42 

Trimethylpentanedioldioic ac., mp. 
120°—44 

Crotonyl eth., bp. 144°—189 

Diisobutylene ald., bp. 230°—20 

Methyldiallylearbinol, bp. 158°—163 


CsH,,0, 


C3H,,03 


C,H,,0, 


C;H,,0; 


CsH,,0 6 
C;H,,O03 


CsH,,0 


C3H,,0, 


Onli gs 


251 


Methylheptenone, bp. 173°—142 
Acetylisocaproyl, bp. 163°—215 
Allyl isovalerianate, bp. 154°—121 
Cycloheptanecarbonic ac., bp. 246° 
-—76 
Ethyleaprolactone, bp. 254°—131 
Ethyl a-ethylcrotonate, bp. 165°— 
122 
Methylhexamethylenecarbonic ac., 
bp. 235°—76 
n-Butyric anhyd., bp. 182°—75 
Ethyl dimethylacetoacetate, bp. 
184°—122 
Ethyl a-propionylpropionate, bp. 
199°—123 
Isobutyric anhyd., bp. 182°—75 
Octanonoiec ac., mp. 29°—39 
Dialdane, mp. 130°—18 
s-Diethylsuccinic acids, mp. 129°, 
192°45, 67 
Diethyl isosuccinate, bp. 198°—123 
Diethyl succinate, bp. 216°—124 
s-Dimethyladipic ac., mp. 140°, 75° 
—62, 40 
Dimethylethylsuccinic 
139°—46 
Dipropyl oxalate, bp. 213°—124 
Isoamylmalonic ac., mp. 93°—42 
Isobutylsuccinic ac., mp. 107°—43 
Pentylmalonic ac., mp. 82°—41 
Suberic ac., mp. 140°—62 
Tetramethylsuccinic ac., mp. 195° 
d.—68 
Diethyl diglycollate, bp. 240°—125 
Diethyl i-malate, bp. 255°—126 
Diethyl tartrate, bp. 280°—126 
Methyl, gallate, + 3H,O, mp. 192°d. 
—119 
Allyl isoamy! eth., bp. 120°—186 
Diethylallylearbinol, bp. 157°—163 
Dimethylhexanone, bp. 151°—142 
Ethyl amyl ket., bp. 170°—142 
Methylbutyrone, bp. 180°—142 
Methylheptenol, bp. 175°—163 
Methylheptanone, bp. 170°—142 
Methyl hexyl ket., bp. 172.5°—142 
Propy] isobutyl ket., bp. 155°—142 
Butyl butyrate, bp. 165°—122 
Caprylic ac., bp. 237°—76 
Dipropylacetic ac., bp. 219°—76 
Ethyl caproate, bp. 167°—122 
Ethyl isobutylacetate, bp. 161°— 
122 
Ethyl diethylacetate, bp. 151°—121 
Ethyl methylpropylacetate, bp. 
153°—121 
Heptyl formate, bp. 176°—122 
Hexyl acetate, bp. 169°—122 
Isoamyl propionate, bp. 160°—122 
Isobutyl butyrate, bp. 157°—122 
Methylcenanthylate, bp. 173°— 
122 
Ethyl ethoxybutyrate, bp. 168°— 
122 


vulpes bith ay 


Ethyl oxydiethylacetate, bp. 175° 
—122 

a-Oxycaprylic ac., mp. 69°—55 

Trimethylpentanoloic ac., mp. 92° 
—42 


252 


C,H,,0 


C,H,3,0, 


C,H, 
C.Hio 


C.His 


FORMULA INDEX. 


Butyl ethers, bp. 141°, 120°—187, 
186 


Diethylisopropylearbinol, bp. 160° 
—163 

Diethylpropylearbinol, bp. 160°— 
163 


Ethyl hexyl eth., bp. 185°—187 
Isobutyl eth., bp. 122°—186 
Methylhexylcarbinol, bp.179°—163 
Methyl heptyl eth., bp. 150°—187 
Methyldipropylearbinol, bp. 161°— 
163 
Octyl ale., bp. 195°—163 
Diisopropylglycol, mp. 51°—155 
Dimethylpinacone, mp. 49°—155 
Ethylidene dipropyl eth., bp. 147° 
—20 


C, GROUP. 


Indene, bp. 1£0°—191 
Phenylallylene, bp. 185°—191 
Benzylethylene, bp. 155°—189 
p-Methylstyrene, bp. 172°—190 
Allylbenzene, bp. 174°—190 
Hydrindene, bp. 176°—190 
Cumene, bp. 153°—1&9 
Propylbenzene, bp. 158°—189 
Methylethylbenzenes, bp. 158°, 162° 
—189, 190 
Mesitylene, bp. 164°—190 
Pseudocumene, bp. 170°—190 
v-Trimethylbenzene, bp. 175°—190 
Nonone, bp. 156°—187 
Campholene, bp. 135°—187 
Trimethyleyclohexene, bp. 138°— 
187 
Dimethylheptadiéne, bp. 142°—187 
Nonylene, bp. 139°—187 
Methvloctene, bp. 141°—187 
Propylhexamethylene, bp. 148°— 
187 
Methylethyleyclohexane, bp 151° 


Dimethyleycloheptane, bp. 153°— 
187 


Hexahydropseudocumene, bp. 135° | 


—1§ 
Mesitylenehexahydride, bp. 136°— 
Hexahydrocumene, bp. 148°—183 
8-Nonane, bp. 130°—183 
a-Nonane, bp. 136°—183 
Nonane, bp. 148°—183 
Trimellitic anhyd. mp. 157°—64 
Truxone, mp. 289°—140 
Coumarin, mp. 67°—129 
Diketohydrinden, mp. 130°—96 
Phenylpropiolic ac., mp. 136°—62 
Cumarilic ac., mp. 192°—67 
Daphnetin, mp. 254°—210 
Aldehydoxyisophthalic acids, mp. 
237°, 260°—18 
Hemimellitic ac., mp. 185° d.—67 
Trimellitic ac., mp. 216° d.—50 
Trimesic ac., mp. 345°, 347°—72, 51 
Cinnamic ald., bp. 130° (20 mm.)— 
21 


Hydrindones, mp. 40°, 61°—136, 
137 
Vinyl phenyl ket., mp. 42°—136 


C,H,0, 


C,H,O, 


C,H,0, 


C,H 305 


C,H,,0 


CoH Oe 


C,H,.9, 


Acetylbenzoyl, bp. 217°—215 
Allocinnamic ac., mp. 68°—55 
Atropic ac., mp. 106°—58 
Cinnamic ac., mp. 1383°—61 
Homococeaic ac., mp. 150°—63 
Isocinnamic ac., mp. 57°—54 
Melilotic anhyd., mp. 25°, bp. 272° 
—129; 132 
Acetophenonecarbonic ac.; mp. 115° 
—bY 
p-Acetylbenzoic ac., mp. 200°—68 
Acetylsalicylic ald., mp. 37°-—17 
Benzoylacetic ac., mp. 103°—58 
Cumaric acids, mp. 191°, 206°, 208° 
—67, 69 
Hydrocumarilic ac., mp. 116°—43 
Phenylpyruvic ac., mp. 154°—63 
p-Toluylearbonic ac., mp. 96°—57 
Acetoxybenzoic acids, mp. 127°, 
185°—60, 67 
Caffeic ac., mp. 195°—209 
Homophthalic ac., mp. 175°—66 
Homoterephthalic ac., mp. 237°—70 
Methylisophthalic ac., mp. 325°— 
72 


Methylphthalic ac., mp. 144°—62 
Methylterephthalic ac., mp. 281°— 
72 


Methoxylphenylglyoxylic ac., mp. 
89°—41 

Monomethylphthalate, mp. 82.5°— 
56 


Phenylmalonic ac., mp. 152°—47 
Salicylic ac. acetate, mp. 118°—59 
Umbellic ac., d. 260°—71 
s-Uvitic ac., mp. 287°—72 
Aldehydovanillic acid, mp. 221°— 
18 
m-Oxyuvitic ac., mp. 290°—72 
p-Anol, mp. 93°—94 
Cinnamyl alc., bp. 254°—165 
Hydrocinnamice ald., bp. 208°—20 
a-Hydroxindene, mp. 54°—157 
Methyl] benzyl ket., mp. 27°-—136 
p-Methyl tolyl ketones, bp. 222°, 
224°—143 
Propiophenone, bp. 218°—143 
Benzyl acetate, bp. 206°—123 
p-Cresyl acetate, bp. 214°—124 
Dimethylbenzoic acids, mp. 98°, 
126°, 132° 144°, 163°, 166°—57, 
60, 61, 62, 65 
Ethylbenzoic acids, mp. 47°, 68°, 
112°—53, 55, 59 
Ethy] benzoate, bp. 212°—123 
Hydrocimean ac., mp. 48.7°— 
54 


Methyl phenylacetate, bp. 220°— 
124 


Pheny! propionate, bp. 211°—123 

Pheriylpropionic ac., bp. 264°—76 

m-Oxybenzoic aldehyde ethylether, 
bp. 245°—21 

Tolylacetic acids, mp. 61°, 88°, 91° 
— 654, 56, 57 

Acetovanillon, mp. 115°—9 

Alorcinic ac., mp. 97°—57 

Atrolactic acid, mp. 90°—42 

Dimethylphenolearbonie ac., mp. 
199°, 223°—68, 70 


C,H, 


C,H,,0, 


C,H,,0, 


C.H,.0, 
C,H,,0, 


C,H,.0, 


FORMULA INDEX. 


Ethoxybenzoic ac., mp. 137°, 195° 
—62, 67 

Ethylether salicylic ac., mp. 19°— 
52 


Ethyl oxybenzoates, mp. 116°, 72° 
—95, 119 

Hydrocumaric acids, mp. 82°, 111°, 
128°—41, 48, 61 

Fluorenecarbonic ac., mp. 175°—66 

Methyl anisate, mp. 45°—118 

Methyl mandelate, mp. 52°—118 

Methylmandelic acids, mp. 84°, 
145°—41, 62 

Methyl methylethersalicylate, bp. 
2235°—125 

Methoxyphenylacetic ac., mp. 72°— 
55 


Methyl oxyphenylacetate, bp. 310° 
—127 


Orcacetophenone, mp. 146°—97 

Oxymesitylenic ac., mp. 179°—66 

Paoénol, mp. 50°—92 

Phenyllactic acids, mp. 93°, 97°-—42 

Phenoxypropionic ac., mp. 112°— 
59 


Phloretic ac., mp. 129°—45 

Tropic acids, mp. 117°, 123° and 
127°—44, 60 

Ethyl-dioxybenzoate, mp. 75°—119 

Hemipinic ac , mp. 161°—64 

Hydrocaffeic ac., mp. 139°—46 

Methy! vanillate, mp. 62°—119 

Phenylglyceric ac., mp. 143°—46 

Veratric ac., mp. 181°—66 

Cyclopentane-tetracarbonic ac., mp. 
187° d.—49 

o-Cresyl ethyl ethers, bp. 180°, 189° 
—191 

Dimethyl] orcinyl eth., bp. 244°— 
193 

Ethyl benzyl eth., bp. 185°—191 

p-Isopropylphenol, mp. 61°—92 

Methylbenzylearbinol, bp. 215°— 
163 

Mesitol, mp. 68°—93 

Phenylpropy] alc., bp. 235°—165 

m-Propylphenol, mp. 26°—91 

Pseudocumenol, mp. 71°—93 

Trimethylphenols, mp. 81°, 95°— 
93, 94 

Methylphenylethyleneglycol, mp. 
§2°—155 

Trimethylbenzoic ald.,mp. 105°—17 

Trimethylphendiole, mp. 149°, 
169°, 156°—97, 99, 98 

Iridol, mp. 57°—92 

Phloroglucin trimethyl eth., mp. 52° 
—175 

Propylpyrogallol, mp. 79°—93 

Mercato trimethyl eth., mp. 47° 
—175 

Ethyl pyrotritarate, bp. 214°—124 

Metacrolein, mp. 45°—17 

Trimethylphloroglucin, mp. 184°— 
99 


Diallylmalonic ac., mp. 1383°—45 
Anhydrocamphoric ae., mp. 1389°— 
46 


Hexamethylenetricarbonic ac., mp. 
152°—47 


253 


Trimethyl aconitate, bp. 270°—126 

Camphenylon, mp. 36°—136 

Diallylacetone, bp. 174°—142 

Phoron, mp. 25°—136 

Campholitic ac., mp. 133°, bp. 241° 
—61, 76 

Ethoxytetrahydrobenzoic ac., mp. 
73°— 55 

Ethyl trimethyleneacetoacetate, 
bp. 226°—124 

Pinonic ac., mp. 128°—61 

Diethyl citraconate, bp. 231°—125 

Diethyl ethylenemalonate, bp. 213° 

”) 


el 


Diethyl glutaconate, bp. 237°—125 

Diethyl itaconate, bp. 228°—124 

Diethyl mesaconate, bp. 229°—125 

Diethyl acetylmalonate, bp. 239°— 
76 


Diethyl ketipate, mp. 76°—93 

Camphoronic acids, mp. abt. 150°, 
166°—47, 48 

Trimethyl citrate, mp. 79°—119 

Ethyldiallylearbinol, bp. 175°—163 

Isobutyl angelate, bp. 177°—122 

Diethylacetylacetone, bp. 203°— 
123 

Ethyl a-butyrylpropionate, bp. 
208°—123 

Ethyl mesitonate, bp. 210°—123 

Ethyl methylethylacetoacetate, bp. 
200°—123 

Azelaic ac., mp. 106°—58 

Diethyl dimethylmalonate, bp. 
196°—123 

Diethyl ethylmalonate, bp. 207°— 
123 


Diethyl glutarate, bp. 237°—125 

Dipropyl malonate, bp. 228°—125 

Dimethylheptanone, bp. 181°—142 

Dipropylacetone, bp. 173°—142 

Ethyl hexyl ket., bp. 190°—142 

Ethyl isoamylacetate, bp. 177°— 
122 


Heptyl acetate, bp. 190°—123 
Isoamyl butyrate, bp. 179°—122 
Isoamy] isobutyrate, bp. 169°—122 
Methyl caprylate, bp. 193°—128 
Octylformate, bp. 193°—123 
Pelargonic ac., bp. 253°—76 
Dibutyl carbonate, bp. 208°—123 
Diisobutyl carbonate, bp. 190°— 
122 
Parapropionic ald., bp. 169°—20 
Ethyldipropylearbinol, bp. 179°— 
163 


Ethyl heptyl eth., bp. 166°—187 

Methyl octyl eth., bp. 173°—187 

Nony]l alc., bp. 213°—163 

Propylidenedipropy] ether, bp. 166° 
—20 


Ethyl orthocarbonate, bp. 158°— 
122 


C,, GROUP. 


Naphthalene, mp. 80°—176 

Phenylcrotonylene, bp. 187°—191 

Ethylphenylacetylene, bp. 202°— 
192 


v-Methylindene, bp. 205°—192 


254 


C,H, 


C,H, 


C, oH, 6 


C,H; 


C,H, 


Cy Ho» 
C,.H,O, 


Up ee 63 
Cy HO, 


Cio H(Os 


CyoH,0 
CioHs02 


Cy) HO; 


FORMULA INDEX. 


Naphthalenedihydride, bp. 212°— 
192 


Butenylbenzene, bp. 186°—191 

Dicyclopentadiéne, mp. 33°—175 

Isobutenylbenzene, bp. 181°—191 

p-Tolylpropylene. bp. 199°—192 

Naphthalenetetrahydride, bp. 205° 
—192 

Phenylbutylene, bp. 177°—191 

Butylbenzenes, bp. 168°, 171°, and 
180°—168, 190, 191 

Cymene, bp. 175°—190 

m-Methylisopropylbenzene, bp.175° 
—190 


Diethylbenzenes, bp. 181°, 182°, and 
185°—191 

Dimethylethylbenzenes, bp. 1°3°, 
185°—191 

Durene, mp. 79°—176 

Naphthalenehexahydride, bp. 205° 
—192 

Tetramethylbenzenes, bp. 196°, 204° 
—192 

Camphenes, mp. 47°, 51°—175 

Decone, bp. 147°—187 

Pinene, bp. 156°—189 

Phellandrene, bp. 171°—190 

Limonenes, bp. 176°, 181°—190, 
191 

Sylvestrene, bp. 176°—191 

Terpinene, bp. 180°—191 

Terpinolene, bp. 184°—191 

Naphthaleneoccahydride, bp. 187° 
—191 

Decenylene, bp. 150°—187 

Dimethylactadiéne, bp. 168°—187 

Propylheptadiéne, bp. 158°—187 

Menthene, bp. 167°—187 

Naphthalenedecahydride, bp. 176°, 
177°—187, 183 

Diamylene, bp. 155°—187 

Dekanaphthene, bp. 161°—183 

a-Terpenetetrahydride, bp. 161°— 
183 

6-Terpenetetrahydride, bp. 164°— 

83 


Terpane, bp. 170°—183 

Decane, bp. 173° c.—183 

Dimethyloctane, bp. 160°—183 

a-Naphthoquinone, mp. 125°—207 

f-Naphthoquinone, d. 117°—206 

Juglon, mp. 152°—208 

a-Dioxynaphthoquinone, mp. 276° 
—211 

Furil, mp. 162°—208 

Naphthazarin—214 

Benzenetetracarbonic acids, 

237°, 238°, 264°—51 

a-Naphthol, mp. 94°—94 

6-Naphthol, mp. 122°—96 

Dioxynaphthalenes, mp. 134°, 140°, 
159°, 178°, 190°—96, 97, 98, 99, 
100 

Hydronaphthoquinones, mp. 60°, 
175°—92, 99 

Indenecarbonic ac., mp. 230°—70 

Methylphenylpropiolic ac., mp. 109° 

59 





Aldehydocinnamie ac., mp. 247°— 
18 





Cio HO, 


Cy HO 


CHO, 


Ci oHsO; 


Cy HO, 


CypH 05 


CoH Oe 
Cy H,,0 


Benzoylacrylic ac., mp. 99°—57 
6-Hydrojuglon, mp. 96°-—96 
Methylcumarilic ac., mp. 188°—67 
Trioxynaphthalene, mp. 120°—95 
Anemonin, mp. 156°—98 
Benzalmalonic ac., mp. 195°—68 
Furoin, mp. 135°—96 
Benzalacetone, mp. 41°—136 
Benzoyltrimethylene, bp. 240°— 
144 
Methylhydrindones, mp. 59°, 63°, 
95°, bp. 246°—137, 138, 144 
Allyl benzoate, bp. 230°—125 
Benzoylacetone, mp. 60°—92 
Benzalpropionic acids, mp. 74°, 82°, 
86°—55, 56 
Butenylonphenol, mp. 139°—97 
Hydrindoncarbonic ac., mp, 130°— 
61 
il attra ac., mp. 257°— 
i 


Tsosafrol, bp. 247°—193 
Methylatropic ac., mp. 135°—61 
Methylcinnamic acids, mp. 115°, 
169°, 197°—59, 65, 68 
Methyl cinnamate, mp. 36°—-118 
Phenylerotonic ac., mp. 65°—55 
Phenyldiacetyl, bp. 175°—215 
Propenylbenzoic ac., mp. 160°—64 
Safrol, bp. 233°—193 
6-Benzoylpropionic ac., mp. 116°— 
59 


Cubebin, mp. 125°—96 
Ethylbenzoylformate, bp. 256°— 
126 


Methy] m-coumarate, mp. 85°—119 

Methoxycinnamic acids, mp. 88°, 
115°, 171°—56, 59, 65 

Benzoyllactic ac., mp. 112°—59 

Benzylmalonic ac., mp. 117°—44 

Dimethy] isophthalate, mp, 64,5°— 
119 


Dimethyl terephthalate, mp. 140°— 
119 

Dimethylterephthalic ac., mp. 206° 
—69 

Dimethyl phthalate, bp. 282°—-126 

Dimethylphthalic ac., mp. 96°—57 

Ferulic ac., mp. 168°—65 

Hydrocinnamocarbonic acids, mp. 
165°, 277°— 65, 71 

Isoferulic ac., mp. 280°—70 

Meconin, mp. 102°—58 

Phenylsuccinic ac., mp. 167°—65 

Dimethyl oxyphthalaets, mp. 96°, 
102°—119 

Opianic ac., mp. 150°—63 

Veratrinketonic ac., mp. 138°—46 

Hemipinic acids, mp. 180°, 161°— 
66, 64 

Anethol, mp, 22°—174 

Benzylacetone, bp. 235°—144 

Anisoin, mp. 142°—179 

Cuminie ald , bp. 235°—20 

Ethyl benzyl] ket., bp. 224°—143 

Ethyl p-tolyl! ket., bp. 238°—144 

Isopropyl phenyl ket., bp. 217°— 
143 


Metanethol, mp. 132°—179 


C,H,,.0, 


CioH205 


C,.H,,0, 
CyoH,,05 
CoH 1206 


Co H205 
C,)H,,0 


FORMULA INDEX. 


Methy! xylyl ketones, bp. 224°, 246° 
—143, 144 
Photoanethol, mp. 207°—180 
Propyl phenyl ket., bp. 221°—143 
p-Lolylacetone, bp. 232°—144 
Trimethylbenzoic aldehydes, mp. 
52°, bp. 237°—17, 20 
Benzylpropionic ac., mp. 47°—53 
Cuminic ac., mp. 116°—59 
Dimethylphenethanoic ac., 
102°-—58 
Etyhlphenylacetate, bp. 229°—125 
Ethylphenylacetic ac., mp. 42°—53 
Ethyl toluates, bp. 221°, 227°—124 
Methylhydrocinnamie ac., mp. 37° 
—53 
Methyl hydrocinnamate, bp. 238° 
125 


Mp. 


Methyl phenylpropionate, bp. 221° 
—124 


Prehnitylic ac., mp. 167.5°—48 

p-Propionylanisol, mp. 27°-—136 

Propylbenzoic acids, mp. 51°, 58°, 
140°—54, 62 

Propyl benzoate, bp. 229°—125 

Tetramethylquinone, mp. 111°— 
206 

Thymoquinone, mp. 45°—205 

Tolylpropionic ac., mp. 102°, 125° 
—58, 60 

Trimethylbenzoic acids, mp. 127°, 
149°, 152°, 215°—60, 63, 69 

Coniferyl ale., mp. 73°—93 

Dimethyldiacetylfurane, mp. 63° 
—176 

Ethyl mandelate, mp. 34°—118 

Ethyl anisate, bp. 269°—126 

Ethyl methylether salicylate, bp. 
235°—125 

Methyl ethylether salicylate, bp. 
245°—125 

Methylethermelilotic ac., mp. 92°— 
57 

Methoethylphenolearbonic acids, 
mp. 71°, 94°, 142°—55, 57, 62 

Methylphenyllactic acid, mp. 95°— 
42 


Oxyisopropylbenzoic ac., mp. 155° 

—64 : 

Phenyloxybutyric ac., mp. 75°—55 

Trimethylphenolmethanoic acids, 
sbl. 148°, 181°—63, 66 

Cantharic ac., mp. 278° c.—71 

Cantharidin, mp. 218°—129 

Ethyl vanillate, mp. 44°—118 

Methyl veratrate, mp. 59°—118 

Ethyl isocarbopyrotritarate, mp. 
110°—59 

Monoethy1 carbopyrotritarate, mp. 
83°—56 

Dimethyl succinylosuccinate, mp. 
152°—97 

Hexamethylenetetracarbonic 
mp. 219° d.—58 

tert.-Butylphenol, mp. 99°—94 

p-Cuminie ale., bp. 247°—165 

Eucarvol, bp. 212°—143 

Tetramethylphenol, mp. 86°, 117°, 
108°—93, 95 

Thymol, mp. 49.6°—92 


ac. dg 


C,oH,,0, 


10°"14~3 


C, oH, Or 


C,»H,.03 


C,H, 0. 


C,oH.05 


C,H, sO, 


255 


Oxythymol, mp. 139°—97 
Camphoric anhyd., mp. 220°—70 


‘Pyrogalloldiethylether, mp. 79°~- 


93 
Camphanic ac., mp. 201°—50, 68 
Diallyl succinate, bp. 249°—126 
Pinoylformic ac., mp. 79°—56 
Camphenic ac., mp. 199°—50 
Tetramethyl — s-ethanetetracarbo- 
nate, mp. 138°—119 
Anthemol, bp. 214°—163 
Camphor, mp. 176°—139 
Citral, bp. 228°—20 
Dihydrocarvone, bp. 221°—143 
Fenchone, bp. 192°—142 
Pinol, bp. 183°—191 
Pulegone, bp. 221°—143 
Thujone, bp. 203°—143 
Campholenic acids, mp. 53°, bp. 
265°—54, 76 
Ethyl diallylacetate, bp. 195°—123 
Trimethyleyclohexenecarbonic ac., 
mp. 106°—58 
Camphylenic ac., mp. 172°—65 
Methoethylolheptanonolid, mp. 63° 
—129 
Pinonic acids, mp. 98°, 103°—57, 


58 

Diethyl allylmalonate, bp. 222°— 
124 

Diisopropyl fumarate, bp. 225°~ 
124 


Camphorie acids, mp. 181° c., 208° 
—66, 69 
Isocamphoric ac., mp. 171°, 191°— 
65, 67 
Cineolic ac., mp. 196° d —68 
Triethylmethanetricarbonate, mp. 
29°—52 
Borneols, mp. 203°, 210°—159 
Coriandrol, bp. 196°—163 
Citronellal, bp. 207°—20 
Diisovalerianic ald., bp. 190°—20 
Eucalyptol, bp. 176°—190 
Geraniol, bp. 229°—163 
Isoborneol, mp. 216°—159 
Linalol, bp. 192°—163 __ 
Menthones, bp. 206°, 207°-—143 
Terpineol, bp. 218°—165 
Camphene glycol, mp. 192°—159 
Campholic ac., mp. 105°—58 
Citronellic ac., bp. 257°—76 
Isoamyl tiglate, bp. 204°—123 
Pinolhydrate, mp. 150°—155 
Dimethyloctanonoic ac., bp. 292° 
6 


Ethyl! diethylacetoacetate, bp. 218° 
—124 


Ethyl isobutylacetoacetate, 
217°—124 

Ethyl methylpropylacetoacetate, 
bp. 214°—124 

Valerianic anhyd., bp. 215°—76, 
131 

Dibutyl oxalate, bp. 243°—125 

Diethyl adipate, bp. 245°—125 

Diethyl s-dimethylsuccinates, bp. 
221°, 232°—124, 125 

yee ethylsuccinate, bp. 225°— 


bp. 


256 


C,,H,.0, 


C,,H,.05 
C, oH,,0 


C,,H.0. 


FORMULA INDEX. 


Diethyl methylethylmalonate, bp. 


207°—-123 
Diethyl propylmalonates, bp. 221°, 
213°—124 
Diisobutyl oxalate, bp. 229°—125 
Dipropy! succinates, bp. 249°, 247° 
—126, 125 
Sebacic ac., mp. 133°—61 
Diisopropyl tartrate, bp. 275°-—126 
Diethyl mucate, mp. 158° d.—119 
Diamylene oxide, bp. 175°—190 
Isocapric ald., 169.6°—20 
Isopropyl hexyl ket., bp. 205°—143 
Menthol, mp. 42°—157 
Methyloctonone, bp. 197°—142 
Propyl hexyl ket., bp. 206°—143 
n-Amyl valerianate, bp. 204°—123 
Capric ac., mp. 31°—52 
Ethyl caprylate, bp. 207°—123 
ee dipropylacetate, bp. 183°— 


Howl butyrate, bp. 205°—123 

Isoamyl isovalerianate, bp. 194°— 
123 

Methyl pelargonate, bp. 213°—124 

n-Octyl acetate, bp. 210°—123 

Ethyl oxycaprylate, bp. 231°—125 

Methyl octyl ket., bp. 211°—143 

Decyl alc., bp. 231°—163 

Diamyl alc., bp. 211°—163 

Ethyl octyl eth., bp. 189°—188 

Isoamyl eth., bp. 173°—187 

Propylhexylearbinol, bp. 210°—163 

s-Dimethy]l dipropyl glycol, bp. 222° 
—165 


s-Tetramethylpinacone, mp. 27°— 


C,, GROUP. 


Methylnaphthalenes, bp. 241°, 242°, 
mp. 32°—193 

Amenylbenzene, bp. 173°—190 

Tolylbutylene, bp. 195°—192 

Amylbenzene, bp. 201°—192 

Butyltoluenes, bp. 177°, 187°-—191 

Diethylphenylmethane, ‘bp. 178°— 
191 

Diethyltoluene, bp. 199°—192 

Dimethylethylphenylmethane, bp. 
190°—191 

s-Dimethylpropylbenzene, bp. 208° 
—192 


Ethylisopropylbenzene, bp. 191°— 
192 


Isoamylbenzene, bp. 193°—192 
Isopropylxylene, bp. 194°—192 
Propylxylenes, bp. 206°, 208°, 209° 
—192 
Pentamethylbenzene, bp. 53°—175 
Undecine, bp. 212°—188 
Undekanaphthene, bp. 190°—183 
Undecylene, bp. 195°—188 
Undecane, bp. 194°—18&3 
Naphthoic ald., mp. 61°—17 
Iso-naphthoic ac., mp. 184° e.—66 
a-Naphthoic ac., mp. 160°—64 
Naphtholcarbonic acids, mp. 169°, 
185°—48, 67 
2- Oxynaphthoic acids, mp. 156°, 
216°, 210°, 235°—64, 69, 70 


C,,H,,0 


C,,H,,05 


C,,H,,0, 


Methylnaphthol, mp. 89°—94 
Methyl a-naphthy! eth., bp. 269°— 
193 
Metay pieny a mp. 41°— 
175 


Naphthylmethyl alcohols, mp. 60°, 
&0°—157, 158 

Nerolin, mp. 72°—176 

Dihydronaphthoic acids, mp. 91°, 
105°, 125°, 161°—57, 58, 60, 64 

Methylindenecarbonic ac., mp. 200° 
—68 

Acetcumaric ac., mp. 146°—63 

Allylacetophenone, bp. 238°—144 

Benzoylcyclobutane, bp. 259°—144 

Cinnamenylpropionic ac., mp. 31— 
52 


Ethyl] cinnamate, bp. 271°—126 

Methylhydrinencarbonic 8C., 5 JG 
80°—56 

Phenylangelic ac., mp. 104°—58 

Phenylpentenoic ac., mp. 104°— 
58 

Tetrahydronaphthoic acids, mp. £5 
94°—56. 57 

o-Ethoxycinnamic acids, mp. 103°, 

135°—5S8, 61 

Ethylbenzoylacetic ACs 
114°—59, 43 

Ethyl p-toluylearbonate, mp. 263° 
—119 


Mpls 


Methyl {-benzoylpropionate, bp. 
290°—127 

Phenyllevulinic ac., mp. 55°—40 

Toluylpropionic ac., abt. 120°—60 

Acetylphenyllactic ac., mp. 100°— 
58 


a-Hydropiperic ac., mp. 75°—55 
Sinapic ac., mp. 189°—209 
p-Acetylcumene, bp. 254°—144 
Acetylmesitylene, bp. 235°—144 
p-Acety Props bp. 259°— 


Butyl phenyl ket.—144 

Ethyl xylyl ketones, bp. 237°, 238° 
—144 

Isobutyl phenylket., bp. 225°— 
144 

Isopropyl] telyl ket., bp. 235°-—144 | 

Methylbenzylacetone, bp. 238°— 
144 

Butyl benzoate, bp. 247°-—125 

Ethylbenzylacetic ac., bp. 272°—76 

Ethyl 1,3- -dimethylbenzoate, bp. 
241° —125 

Ethyl hydrocinnamate, bp. 248°— 
125 

Bees a-phenylpropionate, bp. 230° 

125 


Bihyl m-tolylacetate, bp. 237°— 
12! 


Tahun acids, mp. 127°, 
164°—60, 65 
Isobutyl benzoate, bp. 237°—125 
Methocthylphenethanoic 8C.;. (Tap: 
52°—54 
Methy] ethylphenylacetate, bp.228° 
—125 


Methy! methylhydrocinnamate, bp. 
232°—125 


C,,H oP 


C,,H,,0 


C, iH 2202 


FORMULA INDEX, 


Methylpropylbenzoic ac., mp. 75° 
—55 


Methyl pseudocumy] ket., bp. 246° 
—144 

Phenylvalerianic ac., mp. 58°—54 

Tetramethylbenzoic acids, mp. 165° 
179°—65, 66 

Tolylisobutyric ac., mp. 91°—57 

p-Propionylphenetol, mp. 30°—136 

o-Ethylethermelilotic ac., mp. $0° 
—56 

Ethyl m-ethoxybenzoate, bp. 263° 
—126 

Ethyl ethylethersalicylate, bp. 251° 
—126 

Ethyl o-hydrocoumarate, mp. 34° 
—118 

Phenyloxyvalerianic ac., mp. 131° 

o-Thymotic ac., mp. 123°—60 

Ethyl veratrate, mp. 43°—118 

p-lsoamylphenol, mp. 92°—94 

Isoamyl phenyl eth., bp. 217°—192 

Methyl thymyl eth., bp. 216°—192 

Camphocarbonic ac., mp. 128°—61 

Pentamethylphloroglucin, mp. 114° 
—95 

Undecolie ac., mp. 59.5°—54 

Diethyl pentamethylene dicarbon- 
ate, bp. 251°—126 

Monomethyl camphorate, mp. 86° 
—56 

Phoronic ac., mp. 184°—67 

Triethyl ethenyltricarbonate, bp. 
278°—126 

Undecylenic ac., mp. 24°—52 

Dibutyl malonate, bp. 251°—126 

Diethyl isobutylmalonate, bp. 225° 
—124 

Diethyl isopropyl succinate, bp 
238°—125 

Diethyl diethylmalonate, bp. 223° 
—124 

Diethyl methylpropylmalonate, bp. 
222°—124 

Heptylsuccinic ac., mp. 90°—41 

Diethyl butylmalonate, bp. 233°— 
125 

Diethyl methylisopropylmalonate, 
bp. 221°—124 

Caprone, bp. 226°—144 

Diisoamyl ket. bp. 226°—144 

Methyl nonyl ket., bp. 224°—143 

Ethyl pelargonate, bp. 227°—124 

Isoamyl isobutylacetate, bp. 217° 
—124 

Methyl caprate, bp. 223°—124 

Umbellulic ac. mp. 22°, bp. 277°— 
52 

Undecylic ac., mp. 28°—52 

Diisoamyl carbonate, bp. 229°—125 

Dioxyundecylic ac., mp. 85°—56 


C,, GROUP. 
B-Naphthylacetylene, mp. 36°—175 
Acenaphthylene, mp. 92°—177 
Diphenyl, mp. 70°—176 
Acenaphthene, mp. 95°—177 
$-Ethylnaphthalene, bp. 251°—193 
a-Ethylnaphthalene, bp, 258°—193 


Cy 
C,.Hys 


_ 
iS) 


2.2 
bof 


= 
tb 
i) 
> 


© 
sofas 


[o;) 
to 


ay 
iY) 


ee 
Se) fe) isles fey 


Co 


— fod 
Eh 
Le.) oo 

w 


CROs OCHS 


C,,H,,05 


C,.H,,0; 


257 


Dimethylnaphthalene, bp. 263°— 
» 3193 


allylisopropylbenzene, bp. 229°— 
192 


p-Dipropylbenzene, bp. 220°—192 

Kthylbutylbenzene, bp. 202°—192 

Hexamethylbenzene, mp. 164°— 
179 

Isohexylbenzene, bp. 214°—192 

p-Propylisopropylbenzene, bp. 212° 
—192 


p-Isoamyltoluene, bp. 213°—192 
s-Triethylbenzene, bp. 216°—192 
Dodecon, bp. 197°—188 
Triisobutylene, bp. 178°—187 
Dodekanaphthene, bp. 197°—183 
Duodecylene, bp. 214°—188 
Dodecane, bp. 214°—183 
Acenaphenequinone, mp. 261°-~ 
210 
Mellitic ac., mp. 287°—51 
Acenaphthenone, mp. 121° C.—139 
Biphenylene oxide, mp. 86°—177 
Benzfuril, mp. 41°—205 
Naphthoylformic ac., mp. 113°—43 
Naphthalic ac., mp. 270°—71 
Naphthalenedicarbonic acids, mp. 
d7s007,1/5- 72, 66 
Paracotoin, mp. 152°—208 
Methyl] $-naphthyl ketones, mp. 51° 
295°—137, 145 
Phenyl eth., mp. 28°—174 
Acetylnapthol, mp. 173°—99 
6-Biphenol, mp. 161°—98 
Methyl oxynaphthyl ket., mp. 103° 
—206 
a-Naphthylacetic ac., mp. 131°— 
61 


Methyl $-naphthoate, mp. 77°—119 

Methylphenylfuranecarbonic ac., 
mp. 180°—66 

Dipyrocatechin, mp. 84°—93 

Piperic ac., mp. 216°—210 

Quinhydrone, mp. 171°—208 

Dimethylnaphthol, mp. 185°—96 

Ethyl naphthyl ethers, mp. 37°, 
281°—175, 194 

Methyl cinnamenylvinyl ket., mp. 
68°—137 

Benzalleevulinic ac., mp. 125°—60 

Benzoyltetramethyleneearbonic ac., 
mp. 142°—62 

Diacetylbenzoyl methane, mp. 35° 

91 


Ethyl {-methylcoumarilate mp. 
51°—118 

Triacetylbenzene, mp. 162°—139 

Acetophenonacetacetic ac., mp. 
135°—61 

Ethyl benzoylpyruvate, mp. 43°— 
91 


Benzyllevulinic ac., mp. 98°—57 

Apiol, mp. 30°—174 

Diethyl isophthalate, bp. 285°— 
126 

Diethyl phthalate, bp. 295°—127 

Diethyl terephthalate, mp. 44°— 
118 

Diethyl oxyisophthalate, mp. 52° 
—118 


208 


C,,H,,O, 


C,,H,.O 


C,,H, Oz 


C,,H,.O3 
C,.H,.0; 
Unt; 
Cryo 

Gwe ba ee 


C,,H,,0, 


C,2H290, 
C,,H,,O. 
Cine) 


gee 2us— 7 
Cy 5H O10 ( 


C,,H,.0 
C,,H,.0, 
C,,H,.03 


C,,H 2204 


FORMULA INDEX. 


Diethyl hydroquinonedicarbonate, 
mp. 133°—96 


Dimethyl hemipinate, mp. 61.5°— | 


119 


Diethylacetophenone, bp. 231°— | 


144 
Tsoamyl phenyl ket , bp. 242°—144 
Isopropy! xylyl ket., bp. 289°, 256° 
—144 


Methyl o-cymy] ket., bp. 258°—144 

Methyl duryl ket., mp. 73°, 254°, 
259°—137, 144 

Propyl xylyl ket., bp. 249°, 251°, 
244°—144 

Ethyl cuminate, bp. 240°—125 

Isoamyl benzoate, bp. 261°—126 

p-Isoamylbenzoic ac., mp. 153°— 


Pentamethylbenzoic ac., mp. 210° 


Asarone, mp. 67°—176 
Isoamyl salicylate, bp. 270°—126 


Diethyl carbopyrotritarate, bp. 
284°—126 
Diethyl succinylosuccinate, mp. 
126°—96 
Ethyl thymyl] eth., bp. 227°—192 


Xylitone, bp. 251°—144 

Ethyl diallylacetoacetate, bp. 240° 
—125 

Phloroglucin triethyl eth., mp. 43° 
—175 

Diethyl diacetylsuccinate, mp. 88° 
—94 

Triethyl aconitate, bp. 275°—126 

Dimethyl camphorate, bp. 265°— 
126 

Triethyl tricarballylate, bp. 300°— 
127 

Triethyl citrate, bp. 294°—127 


?) Dextrin, —29 


Inulin—31 

Diallyl eth., bp. 180°—187 

Hexenyl eth., bp. 117°—186 

Methyl undecylenate, pb. 248°— 
126 

Diethylacetic anhyd., bp. 230°—76 

Ethyl dipropylacetoacetate, bp. 
235°—125 

Lanolic ac., mp. 76°—55 

Diethyl isoamylmalonate, bp. 241° 

—125 

Diethyl suberate, bp. 284°—126 

Diisoamyl oxalate, bp. 263°—126 

Diisobutyl succinate, bp. 265°—126 

Dimethyl sebacate, mp. 38°—118 

Diisobutyl tartrate, mp. 68—119 

Lactose—29 

Maltose—29 

Saccharose, abt. 160° d.—29 

Lauric ald., mp. 44°—17 

Diisoamylacetic ac., mp. 46°—53 

Ethyl caprate, bp. 244°-125 

Lauric ac mp. 43.6°—53 

Diisoamyloxalic ac., mp. 122°—60 

Paraisobutyric aldehyde, mp. 59°- 
60°—17 

Dodecy] ale., mp. 24°—157 

Ethylidenediisoamyl eth., bp. 211° 





C,3H,,03 


C,3H,.O, 
C,,H Os 
C,3H,,0 


C,,H,,0, 


C,, GROUP. 


Sequoiene, mp. 105°—178 

Fluorene, mp. 112°—178 

y-Methylenebiphenyl, mp. 116°— 
178 


Phenyltolyl, bp. 259°—193 

Diphenylmethane, bp. 261°—193 

p-Phenyltolyl, bp. 265°—193 

m-Phenyltolyl, bp. 275°—193 

Diphenylmethane, mp. 26°—174 

-Propylnaphthalene, bp. 265°— 
193 


Heptylbenzene, bp. 233°—193 
Tridekanaphthene, bp. 209°—C, ,H,, 
Tridecylene, bp. 233°—188 
Tridecane, bp 234°—183 


60)o (?) Galloflavin—213 
O 


Diphenylene ket., mp. 84°—205 

Isodiphenylene ket., mp. 83°—138 

Pseudodiphenylene, ket. mp. 85°— 
205 


Pyrene ket., mp. 142°—207 
Fluorenequinone, mp. 181°—209 


. Xanthone, mp. 173°—180 


Oxyxanthones, mp. 146°, 231°-- 
207, 210 

Euxanthone, mp. 240°—210 

Benzophenone, mp. 48°—137 

Benzophenone allotropic, mp. 20.6° 
—136 

Fluorene alc., mp. 153°—159 

Xanthene, mp. 100°—177 

p-Benzoylphenol, mp. 134°—96 ~ 

Naphthylacrylic ac., mp. abt. 210° 
—69 


Oxybenzophenones, mp. 40°, 116°— 
91, 95 

Phenyl benzoate, mp. 68°—119 

Phenylbenzoic ac., mp. 110°, 160°, 
218°—59, 64, 70 

Benzohydroquinone, mp. 125°—206 

Benzopyrocatechin, mp. 145°—97 

Benzoresorcin, mp. 144°—97 

Dioxybenzophenones, mp. 59°,143°, 
162°—98, 205, 207 

Diphenyl carbonate, mp. 78°—119 

Euxanthoic ac.. mp. 201°—209 

Phenylethersalicylic ac., mp. 113° 
—59 

Phenoxybenzoic ac., mp. 159°—64 

Phenyl p-oxybenzoate, mp. 116°— 
99 


Salol, mp. 42°—91 

Alizarine yellow A, mp. 140°—207 

Salicyloresorcin, mp. 133°—207 

Tetraoxybenzophenone, mp. 149° 
—208 

Benzhydrol, mp. 68°—157 
-Benzylphenoj, mp. 84°—93 
henyl benzyl eth., mp. 38°—175 

Propanoylnaphthene, bp. 306°— 
145 


Benzhydroxylphenol, mp. 161°— 
98 
Dioxydiphenylmethane, mp. 158° 
8 


Ethyl 8-naphthoate, bp. 309°—127 
Ethyl a-naphthoate, bp. 309°—127 
Ethylnaphthoic ac., mp. 132°—61 


NOTE ON REAGENTS FOR REDUCTION TESTS. 
(To face page 17 of ‘‘ The Identification of Commercial Dyestuffs.”’) 


While the original descriptions of all color discharges obtained in Tests 8 and 11 
that are tabulated in Volume III are basea on the use of a solution of Rongalite C, 
practically identical results under the same experimental conditions are secured by 
the employment of a reducing mixture prepared by the following empirical procedure: 

Place in a 300-cc. flask 15 grams of dry sodium bisulphite and 8 grams of zine 
dust. Add 75 cc. of distilled water. Shake to dissolve the bisulphite and wet the 
zine. Then add from a burette 7.5 cc. of commercial “ formalin ”’ (40 per cent formic 
aldehyde solution). After mixing thoroughly, heat quickly to boiling on a wire gauze 
over a Bunsen flame, and boil moderately for just 5 minutes. Dilute at once with 
45 cc. of cold distilled water, and then cool and filter. Or, double all the quantities 
mentioned may be taken, and the mixture boiled for the same period of 5 minutes. 

The commercial dry sodium bisulphite of the quality placed on the American 
market by reputable manufacturers as the ‘‘ U.S.P. viii’’ grade, if taken from full 
recently purchased bottles, is generally suitable for the preparation of this reagent, 
even when not absolutely fresh. The finished reagent should not be preserved for 
more than a few days, and should not smell of formic aldehyde when warmed. It 
should be understood that the times required for discharges in reduction tests and 
the color-returns in oxidation tests as stated in the tables are only approximations, 
and will be found to vary slightly in independent experiments with the same dyestuff 
whichever reagent is employed. 

In Tests 6, 11, and 21 it is permissible to substitute any good commercial sodium 
hydrosulphite for Blankit T. 


y 


‘i 
o 








C,H,,0 


C,,H wOs 
C, 3H,,0, 
C,H, .O, 


132-16 7 
13°18 


C,H, 


C,H 16 


Ci, HL, 


FORMULA INDEX. 


Camphorphoron, bp. 202°—143 

Ditetramethylene ket., bp. 204°— 
143 

Ethyl benzalacetoacetate, mp. 59° 
—118 

Ethyl benzoylacetoacetate, mp. 27° 
—118 

Diacetylmesitylene, mp. 46°—137 

Helicine, mp. 175°—18 

Cumylacetone, bp. 262°—145 

Methyl pentamethylphenyl ket., 
mp. 85°—138 

Phenyl hexyl] ket., bp. 271°—145 

Ethyl cymy] ket., bp. 267°—145 

Hexyl benzoate, bp. 272°—126 

Salicin, mp. 201°—100 

Ethyl camphocarbonate, bp. 276° 
—126 

Diethyl diallylmalonate—125 

Ethyl undecylenate, bp. 259°—126 

Brassylic ac.. mp. 112°—59 

Diethyl azelate, bp. 291°—127 

Diisoamylmalonic ac. mp. 147°— 
63 

Dihexyl ket., mp. 30°—136 

Methyl undecyl ket., mp. 28°—136 

Tridecylic ac., mp. 40°—53 

Dihexylearbinol, mp. 41°—157 


C,, GROUP. 


Anthracene, mp. 216° c.—180 
TIsoanthracene, mp. 134°—179 
Phenanthrene mp. 100°—177 
Tolane, mp. 60°—176 
Anthracenedihydride, mp. 108°— 
178 
a-Diphenylethylene, bp. 277°—194 
Stilbene, mp. 124°—178 
m-Benzsyltoluene, bp. 275°—193 
Dibenzyl, mp. 52°—175 
Di- or Bitolyl, bp. 275°, 280°, 288°, 
mp. 121°—193 194, 173 
m-Ethylbiphenyl, bp. 283°—194 
Phenanthrenetetrahydride, bp. 310° 
—194 
Anthracenehexahydride, mp. 63°— 
176 
Diphenylpropane, bp. 280°—194 
Isobutylnaphthalene, bp. 280°— 
194 
tert. Dibutylbenzene mp. 70°—176 
Diisobutylbenzene, bp. 235°—193 
Octylbenzene, bp. 262°—193 
Tetraethylbenzene, bp. 250°, mp. 
13°—192, 174 
Perhydroanthracene, mp. 88°—177 
Phenanthreneperhydride, bp. 272° 


—193 
Tetradecine(4), mp. 6°—174 
Tetradekanaphthene, bp. 243°— 
183 


Tetradecane bp. 252°—183 

Anthraquinone, mp. 273°—211 

Isoanthraquinone, mp. 211°—209 

Phenanthrenequinone, mp. 202°— 
209 

Diphenyleneketonecarbonic acids, 
mp. 191°, 227°-—209, 210 

m-Oxyanthraquinone, mp. 302°— 
211 





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Alazarin, mp. 289°—211 

Anthraflavic ac.—213 

Anthrarufin, mp. 2¢0°—211 

Benzdioxyanthraquinone, mp. 292° 
—211 

Dioxyanthraquinone—214 

Isoanthraflavic ac.—212 

Xanthopurpurin, mp. 262°—210 

Anthragallol, mp. 310°—211 

Flavopurpurin—212 

TIsopurpurin—2Z14 

Purpurin, mp. 256°—210 

Alizarin Bordeaux—214 

Alizarincyanin ‘‘R’”’—214 

Rufigallic ac.—214 

Anthranol, mp. 165°—99 

Phenanthrol, mp. 112°—95 

Benzil, mp. 95°—206 

Dioxyanthracene, d. 220°—210 

Dioxyhydrobenzoin - diesoanhydr., 
mp. L1G 1 7s 

Dioxyphenanthrene, mp. 143°—97 

Diphenylene acetic ac., mp. 221°— 
70 


Fluorenecarbonic ac., mp. 175°—66 

Fluorenic ac., mp. 245°—71 

Benzoic anhyd., mp. 42°—53 

Benzoylbenzoic acids, mp. 93°, 161°, 
194°—57, 64, 67 

Diphenyleneglycollic ac., mp. 162° 
—65 


Disalicylic ald., mp. 128°—18 
Benzoylperoxide, mp. 103°—129 
Diphenic ac., mp. 229°—70 
Diphenyl oxalate, mp. 130°—119 
Gentianine, mp. 267°—210 


C,,H 
C,,H,,0,(?) Gallotannic ac., mp. abt. 210°—50 
C,H 


Acetylbiphenyl, mp. 121°—139 

Desoxybenzoin, mp. 60°—137 

Dihydroanthranol, mp. 129°—96 

Oxystilbene mp. 135°—97 

Phenyltolyl ket., mp. 49°—bp. 315° 
—137. 145 

Benzoin, mp. 133°—139 

Benzyl benzoate, bp. 323°—127 

Benzylbenzoic acids, mp. 107°, 114°, 
154°—58, 59, 63 

Diphenylacetic ac., mp. 148°—63 

Methyl phenylbenzoate, bp. 308°— 
127 

Oxyhydroanthranol, mp. 99°—94 

Phenyltolyl carbonic ac., mp. 243° 
—70 

Tolylbenzoic ac., mp. 204°—68 

Benzilic ac., mp. 150°—63 

Methyl phenylethersalicylate, bp. 
a. 360°—127 

Phenylethermandelic ac., mp. 108° 

5 


—58 

Phenyl methylethersalicylate, mp. 
59°—118 

Cotoin, mp. 180°—207 

Benzyl eth., bp. 296°—194 

Isopropyl! naphthy] ket., bp. 309°— 
145 


Propyl naphthyl ket., mp. 50°—137 

Phenylbenzylearbinol, mp. 42°— 
157 

Phenyltolylearbinol, mp. 52°—157 

Cresyl eth., mp. 50°—175 


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FORMULA INDEX. 


Bicresol, mp. 161°—98 

Ethylene diphenyl eth., mp. 98°— 
177 

Hydrobenzoin, mp. 188°—158 

Isohydrobenzoin, mp. 119°—158 

p-Diphenolethane, mp. 122°—96 

Curcumin, mp. 178°—208 

Ethyl piperate, mp. 77°—119 

Diethyl benzalmalonate, mp. 32°— 
118 

Filixic ac., mp. 184°—99 

Tolvl hexyl ket., mp. 42°—136 

Tetraethyl ethylenetetracarbonate, 
mp. b/ 11s 

Diethyl camphorate, bp. 285°—126 

Dicenanthylie ald., bp. 279°—20 

Ethyl diisobutylacetoacetate, bp. 
251°—126 

(Enanthylic anhyd., bp. 269°—132 

Diethyl sebecate, bp. 307°—127 

Diisoamy] succinate, bp. 295°—127 

Dodecanedicarbonic ac., mp. 123°— 
60 

Myristic ald., mp. 52°—17 

Tetradecanone (2), mp. 33°—136 

Amylheptylacetic ac., bp. 305°— 
76 


Ethyl laurate, bp. 269°—126 
Myristic ac., mp. 54°—54 
Oxymyristic ac., mp. 51°—54 
Heptyl eth., bp. 261°—188 
Tetradecyl alc., mp. 38°—157 


C,, GROUP. 


Fluoranthene, mp. 109°—178 

Methylanthracenes, mp. 199°—180 

Isomethylanthracene, mp. 203°— 
180 

Phenyltolylethylene, mp. 118°— 
178 


Benzyl-p-xylene, bp. 294°—194 

Benzyltolylmethane, mp. 27°—174 

Dimethyldiphenylmethane, bp. 281° 
—194 

Ditolvlmethanes, bp. 286°, mp. 22° 
—194, 174 

Ethylbenzylbenzene, bp. 294°—194 

p-Phenyltolylethane, bp. 286°—194 

Sesquiterpenes, bp. 250°-280°—193 

Cadinene, bp. 275°—193 

Benylene, bp. 225°—192 

Pentadekanaphthene, bp. 247°— 
183 

Triamylene, bp. 233°—188 

Pentadecane, bp. 270°—183 

Fluoranthenequinone, mp, 188°— 
209 

Anthraquinonecarbonic ac., 
283°—211 

Alizarincarbonic ac., mp. 305°—211 

Purpurinxanthincarbonic ac., mp. 
231°—210 

Purpurincarbonic ac., mp. 219°— 
210 

Anthracenecarbonic ac., mp. 206° 
—209 

Methylanthraquinone, mp. 177°— 
203 

Phenanthrenecarbonic acids, mp. 
251°, 266° —71 


mp. 





C, 5H 003 
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Diphenylpropanetrione, mp. 69°— 
205 

Chrysophanic ac., mp. 178° (?)— 
208 


Dioxyflavone, mp. 275°—211 

Fisetin—213 

Luteolin—213 

Quercetin—213 

Benzylideneacetophenone, mp. 57° 
137 

Phenylindanone, mp. 78°—138 

Dibenzoylmethane, mp. 81°—93 

Phenylcinnamic ac., mp. 172°—65 

Phenyl cinnamate, mp. 72°—119 

Stilbenecarbonic ac., mp. 159°—64 

Toluylbenzoic ac., mp. 146°—63 

Diphenylmethanedicarbonic _ac., 
mp. 290°—72 

Benzylacetophenone, mp. 72°—137 

Dibenzyl ket., mp. 34°—136 

s-Dimethylbenzophenone, mp. 92° 
—138 

p-Ethylbenzophenone, bp. a. 300° 

145 


Phenyl xylyl ket., mp. 36° 94°, bp. 
322°—136, 188, 145 
Methyldiphenylacetic ac., mp. 178: 
65 


Ethyl phenylbenzoate, bp. 314°— 
127 


Phenyltolylacetic ac., mp. 115°—59 
Benzoylveratrol, mp. 99°—138 
Diphenyllactic ac., mp. 159°-—64 
Lapachol, mp. 140°—207 

Methyl benzilate, mp. 74°—119 
Benzocotoin, mp. 98°—94 
Oxylapachol, mp. 127°—207 
Peucedanin, mp. 109°—119 


C,;H,,0, (?) Santalin, mp. 104°—206 


15°16 

C,5H,,0, 
C,5H,,0, 
C 5H,,03 
C,sH03 
C,5H..0, 
C,H, 

C,5H..0, 


Dibenzylearbinol, bp. 327°—165 
Ditolylearbinol, mp. 69°—157 
Diphenyloldimethylmethane, 
151°—97 
/Esculin, mp. 160°—98 
Daphnin, mp. 200°—100 
Perezinon, mp. 143°—207 
Santonin, mp. 169°—129 
Pipitzahoic ac., mp. 103°—206 
Santanous ac., mp. 178°—66 
Oxypipitzahoic ac., mp. 130°—207 
Santonic ac., d. 120°—60 . 
Isobutyl isocymyl] ket., bp. 271°— 
145 


mp. 


Octyl benzoate, bp. 305°—127 
Octylbenzoic ac., mp. 139°—62 
Alantolic ac., mp. 94°—57 
Photosantonic ac., mp. 154°—63 
Ledum camphor, mp. 104°—138 
Cimicic ac., mp. 44°—53 

Dihepty: ket., mp. 40°—136 . 
Methyl tridecy] ket., mp. 39°—136 
Pentadecylic ac., mp. 51°—54 
Oxypentadecylic ac. mp. 51°—54 


C,, GROUP. 


Diphenyldiacetylene, mp. 88°—177 

Pyrene, mp. 148°—179 

Phenylnaphthalenes, bp. 324°, mp. 
102°—194 178 


C,,H,; 


C,.H,,0, 
C, eH,.0. 


C,.H, Os 


FORMULA INDEX. 


Dimethylanthracenes, mp. 71°, 231°, 
246°—176, 180, 181 
Diphenylbutadiéne, mp. 148°—178 
Ethylanthracene, mp. 60°—176 
Dimethylanthracenehydride, 
181°—180 
Dimethylstilbene, mp. 179°—180 
Diphenylbutene, mp. 39°—175 
Distyrene, mp. 124°—178 
Ethyl] stilbene, mp. 89°—177 
Ditolylethylene, bp. 304°—194 
Benzylmesitylene, mp. 36°—175 
s-Benzyltolylethane, bp. 293°—194 
Dimethyldiphenyl ethane, mp. 123° 
—178 
s-Diphenylbutane, mp. 52°—175 
Ditolylethane, bp. 296°—194 
Di-p-xylyl, mp. 125°—178 
p-Ethyldibenzyl, bp. 294°—194 
Methylethyldiphenylmethane, mp. 
128°—178 
Diisoamylbenzene, bp. 265°—193 
Pentaethylbenzene, bp. 277°—193. 
Cetylene, bp. 282°—188 
Hexadecine(1), mp. 15°—174 
Cetene, bp. 274°—188 
Hexadecane, bp. 287°—183 
Dimethyltetradecane, bp. 268° c.— 
183 
Pyrenequinone, mp. 282°—211 
Biphthaly]l, mp. 334°—130 
Anthraquinonedicarbonic ac., mp. 
340°—211 
Phenylnaphthoquinone, mp. 109°— 
206 


mp. 


Stilbenedicarbonic anhyd., 
155°— 64 

Diphenylfurfurane, mp. 91°—177 

Methyl anthracenecarbonate, mp. 
111°—119 

Phenacetolin—213 

Dibenzoylacetic ac., mp. 109°—59 

Diphenylbutanoltrione, mp. 170°— 
208 

Brazilein—212 


mp. 


Diphenylmethanetricarbonic ac., 
mp. 219°—70 

Hemateine—214 

Piperonyloine, mp. 120°—139 

Dimethyldihydroanthrenone, mp. 


93°—138 
Diphenylbutanedione, mp. 144°— 
139 
Toluic anhyd., mp. 36°—53 
Bibenzyldicarbonic ac., mp. 252°— 
71 
Diphenyl succinate, mp. 118°—119 
Diphenylsuccinic ac., mp. 183°— 


66 
Ethyl benzosalicylate, mp. 79°— 
119 
Hematoxylin, mp. 140°—207 
Protocotoin, mp. 141°—97 
Benzoinethylether, mp. 95°—138 
Benzyltolylacetic ac., mp. 95°—57 
Dibenzylacetic ac., mp. 87°—56 
Ethyldiphenylacetic ac., mp. 173° 


—65 
Dihbenzyleglycollic ac., mp. 157°—64 
Ethyl benzilate, mp. 34°—118 


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Anisoin, mp. 109°—138 
Methylhydrocotoin, mp. 115°—138 
Acetophenonepinacone, mp. 120°— 
158 
Hydranisoin, mp. 170°—159 
Hydroceerulignon, mp. 190°—100@ 
Barbaloin, mp. 147°—207 
Coniferine, mp. 185°—100 
Palmitolic ac., mp. 47°—53 
Palmitoxylic ac., mp. 67°—55 
Hypogeic ac., mp. 33°—52. 
Caprylic anhyd., bp. 285°—132 
Oxyhypogeic ac., mp. 34°—53 
Agaricic ac., mp. 142°—62 
Hexadecanone(2), mp. 48°—137 
Palmitie ald., mp. 58°—17 
Diheptvlacetic ac., mp. 26°—52 
Ethyl myristate, bp. 295°—127 
Palmitic ac., mp. 63°—54 
Lanopalmitic ac., mp. 87°—56 
a-Oxypalmitic ac., mp. 82°—56 
Dioxypalmitic ac., mp. 115°—59 
Cetyl alc., mp. 50°—157 
Octyl eth., bp. 294°—188 
Cetene glycol, mp. 75°—157 
Isoamyl orthoformate, bp. 266°— 
126 


C,, GROUP. 
a-Benzylnaphthalene, mp. 59°— 
176 


Trimethylanthracenes, mp. 222°, 
227°, 243°—180 
Isopropylstilbene, mp. 84°—177 
Retenefluorene, mp. 97°—177 
Benzyleymene, bp. 308°—-194 
Benzylduryl, mp. 60°, 145°—176, 
179 
Phenylxylylpropane, bp. 324°—194 
Heptadecane, mp. 22°—174 
Chrysoketone, mp. 133°—207 
Pyrenecarbonic ac., mp. 267°—71 
Chrysofluorene, ale., mp. 166°—159 
Phenyl naphthyl ketones, mp. 75°, 
82°—137, 138 
Chrysenic ac., mp. 186°—67 
Cinnamylene acetophenone, 
102°—206 
Dibenzylideneacetone, mp. 112°— 
206 
Atronic ac., mp. 164°—65 
Isatronic ac., mp. 156°—64 
Acetonephenanthrene ket., mp. 90° 
—205 
Dibenzoylacetones, mp. 82°, 108°— 
93, 138 
Retene ket., mp 90°—205 
Diphenylglutaric ac., mp. 164°—65 
Retenefluorene ale.. mp. 183°—158 
Ditolylpropionic ac., mp. 151°—63 
Carminic ac.—212 
Diethyldiphenolmethane, mp. 199° 
—100 
Podocarpic ac., mp. 187°—67 
Roccellic ac., mp. 132°—61 
Oxyroccellic ac., mp. 128°—60 
Diheptylacetone, bp. 302°—145 
Methyl quindecyl ket. mp. 48°— 
137 


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FORMULA INDEX. 


Margaric ac., mp. 60°—54 
Daturic ac., mp. 54°—54 
Methy! palmitate, mp. 28°—118 


C,, GROUP. 


Chrysene, mp. 250°—181 
Isochrysene, mp. 196°—180 
Naphthanthracene, mp. 141°—179 
Truxene, mp. a. 360°—-181 
Diphenylbenzene, mp. 205°—180 
Retene, mp. 98°—177 
Tetramethylanthracene, mp. 231° 
—180 
Jsobutylanthracene, mp. 57°—175 
Diethylstilbene, mp. 134°—179 
Tetramethylanthracenehydride, mp 
171°—179 
Tetramethylstilbene, mp 105°, 157° 
—179, 178 
Diethylanthracenedihydride, 
49°—175 
Dixylylethane, bp. 324°—194 
Hexaethylbenzene, mp. 129°—178 
Tributylbenzene, mp. 128°—178 
Octadecines, mp. 26°, 30°—174 
Anthemene, mp. $3°—176 
Octadecylene, mp. 18°—174 
Octadecanes, mp. 28°, bp. 317° e.— 
174, 183 
Chrysoquinone, mp. 235°—210 
Naphthoylbenzoic ac., mp 173°— 


mp. 





66 
Oxynaphthoylbenzoic ac., mp. 256° 
=i 


Phenylbenzoylpyronone mp. 171° 
—208 

Diphenylfurandicarbonic ac., mp. 
238°—70 

Pulvic ac., mp. 214°—209 

Benzyl! naphthyl ket., mp. 57°-—137 

Cinnamic anhyd., mp 132°—61 

Pyrogalloquinone—214 

Octylene oxide, bp. 145°—187 

Retenequinone, mp. 198°—209 

Isoatropic acids, mp. 206°, 237°— 
69, 70 

Phenoquinone, mp. 71°—205 

Truxillic acids, mp. 228°, 274°—70, 
71 

Carbousnic ac., mp. 200°—209 

Usnic ac., mp. 195°—209 

Trigenin, mp. 186°—100 

Ditoluylethane, mp. 159°—139 

Dibenzylacetoacetic ac., mp. 89°— 
56 


Diethyl diphenate, mp. 42°—118 

Hexamethyl mellitate, mp. 187°— 
119 

Methyltolylpinacone, mp. 90°—158 

Camphoronic anhyd., mp. 175°—66 

Stearolic ac., mp. 48°—53 

Ricinostearolic ac., mp. 51°—54 

Ricinelaidic ac., mp. 50°—54 

Ricinstearoxylic ac. mp. 78°—56 

Stearoxylic ac., mp. 86°—56 

Raffinose, mp. 118°—29 

Elaidic ac., mp. 51°—54 

Isoéleic ac., mp. 44°—53 

Oleic ac., mp. 14°—52 





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Ricinoleic ac., mp. 16°—52 
Ketostearic ac., mp. 84°—56 
Dioxyricinoleic ac., mp. 64°—55 
Octadecanone mp. 51°—137 
Stearic ald., mp. 63°—17 
Ethyl diheptylacetate, bp. 310°— 
127 
Ethyl palmitate, mp. 24° - 118 
Stearic ac., mp. 69°—55 
Oxystearic acids, mp. 84°—56 
Dioxystearic acids, mp. 995 136° 
142°—57, 62 
Trioxystearic ac., mp. 141°—62 
Tetraoxystearic ac., mp. 173°—65 
Octadecyl ale., mp. 59°—157 


C,, GROUP. 


Biphenylenediphenylmethane, mp 
145°—179 
Phenylenediphenylmethane, mp. 
148°—179 
Benzyldiphenyl, mp. 85°—177 
Triphenylmethane mp. 92°—177 
IJsoamylanthracene, mp. 59°—176 
Diphenylheptane, bp. 14°—174 
Nonadecane, mp. 32°—175 
Aurine, 213 
Phenyl phenylethersalicylate, mp. 
109°—119 
Phenyl phenoxybenzoate, mp. 75° 
—119 


Vulpic ac., mp. 148°—208 
Trioxyaurine—212 
Resaurine—213 
Triphenylearbino], mp. 162°—159 
Cinnamylenebenzylideneacetone 
mp. 106°—206 
Dioxytriphenylmethane, mp. 161° 
—98 
Benzaurine—214 
Tetraoxytriphenylmethane, mp. 
171°—99 
Euxanthic ac., mp. 157°—208 
Abietic ac., mp. 153°—63 
Lichen-stearic ac., mp. 124°—60 
Dioctylmalonic ac., mp. 75°—55 
Cetylmalonic ac., mp. 122°—60 
Dinonyl ket., mp. 58°—145 
Dioctylacetone, bp. 327°—145 
Methyl heptadecyl ket., mp. 56°— 
137 
Methyl stearate, mp. 38°—118 
Nondecylic ac., mp. 66°—55 
C,, GROUP. : 
Dinaphthyls, mp. 79°, 187°, 154°— 
176, 180, 179 
Phenylanthracene, mp. 152°—179 


Benzylfluorene, mp. 102°—178 
Diphenyltolylmethane, mp. 128°— 
178 


Phenylanthracenedihydride, 
120°—178 

Dibenzylbenzenes, mp. 78°, 86°— 
176; re 

Diphenyltolylmethanes, mp. 59° 
71°—176 

Methyltriphenylmethane, mp. 62° 

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Triphenylethane, bp. 397°—194 


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FORMULA INDEX. 


Hexamethylstilbene, 161°— 
179 

Diterebenthyl, bp. 344°—194 

Diterpenes, bp. a. 300°—194 

Dicamphenehydride, mp. 94°—177 

Hicocylene, bp. 314°—188 

Tetraamylene, bp. 395°—194 

Eicosane, mp. 37°—175 

Coeruleine—214 

Galleine—214 

Dinaphthalene oxides, mp. 184°— 
——180; 161°—179 

Hydroquinonephthalein, mp. 202° 
—100 

Fluoresceine—213 

Naphthylnaphthoquinone, 
177°—208 

Naphthyl ethers, mp. 105°, 110°, 
161°—178, 179 

Phenyloxanthranol, mp. 208°—139 

Phenylene diphenyl! ket., mp. 100° 


—138 
Terephthalophenone, mp. 159°— 
139 


mp. 


m p. 


Diphenyl phthalate, mp. 70°—119 

Fluorescine, mp. 125°—60 

Resorcinoxalein—212 

Triphenylacetic ac., mp. 264°—71 

Triphenylmethanecarboniec acids, 
mp. 161°, 162°—64 

Rosoliec ac.—213 

Triphenylearbinolcarbonic ac., mp. 
200°—68 

Resorcinphenylacetein, mp. 267°— 
210 

Diphenyltolylearbinol, mp. 150°— 
159 


Phenolphthalol, mp. 190°—100 
Diacetyldibenzylethane, mp. 174° 
—139 
Scoparin, mp. abt. 210°—209 
Ethyl dibenzylacetoacetate, 
57°—118 
Benzoylsalicin, mp. 180°—99 
Bithymoquinone, mp. 200°—209 
Cuminyl eth., bp. 350°—194 
Bicarvacrol, mp. 154°—98 
Bithymol, mp. 165°—99 
Absinthin, mp. — 122°—206 


mp. 


6 (2?) Cholanic ac., mp. 285°—72 


Cupreol, mp. 140°—158 
Quebrachol, mp. 125°—158 
Eikosinic ac., mp. 69°—55 
Lithofellic ac., mp. 204°—68 
Eikosenic ac., mp. 50°—54 
Arachidic ac., mp. 77°—55 
Ethyl stearate, mp. 34°—118 
Eikosanoloic ac., mp. 91°—57 


C,, GROUP. 


Benzylphenanthrene, mp. 155°— 
179 

Dinaphthylmethane, mp. 92°—177 

Methylphenylanthracene, mp. 119° 
—176 

Phthalacene, mp. 173°—180 

Dibenzyltoluene, bp. 394°—194 

Phenylditolylmethane, mp. 55°— 
175 


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Heneicosane, mp. 40°—175 

Picylene, ket. mp. 185°—209 

Dinaphthyl ket., mp. 1385°—139 

Picenic ac., mp. 201°—68 

Methylenedinaphthol, mp. 194°— 
100 

Phenyldibenzoylmethane, mp. 119° 

9 


Resorcincinnamyleine—214 


Triphenylmethanedicarbonic  ac., 
mp. 278°—72 

Dicinnamenyl vinyl ket., mp. 142° 
—207 


Methyltriphenylmethanecarbo nie 
ac., mp. 203°—68 

Methyltriphenylmethanecarbonic 
ac., mp. 217°—70 

Tolyldiphenylmethanecarbonic ac., 
mp. 154°—63 

Triphenylpropionic ac., mp. 177°-— 
66 


Dioxydimethyltriphenylme thane, 
mp. 170°—208 
Phloridzin, mp. abt. 170°—99 


C,. GROUP. 


Picene, mp. 364° c.—181 

Dinaphthylethylene, mp. 149°—179 

Dinaphthostilbene, mp. 161°—179 

Dinaphthylethanes, mp. 136°, 160°, 
253°—179, 181 

Dixylvlbenzenes, bp. 394°—194 

Cetylbenzene, mp. 27°—174 

Docosane, mp. 44°—175 

Naphthoic anhydrides, mp. 133°, 
145°—61, 62 

Dibenzoylstyrene, mp. 129°—207 

Triphenylbutanedione, mp. 126°— 
139 

Orcinaurine—212 

Cresolaurine—212 

Diethyl truxillate, mp. 146°—119 

Dithymolethane, mp. 185°—100 

Anacardic ac., mp. 26°—52 

Phenyl pentadecyl ket., mp. 59°— 
137 

Cholestol, mp. 139°—158 

Illicyl ale.. mp. 175°—159 

Behenolic ac., mp. 57°—54 

Brassidic ac., mp. 60°— 54 

Erucic ac., mp. 33°—53 

Isoerucic ac., mp. 55°—54 

Behenic ac., mp. 84°—56 

Oxybehenic ac., mp. 96°—57 

Isodioxybehenie ac., mp. 98°-—57 


C,, GROUP. 


Benzylnaphthalene, mp. 35°—175 

Dibenzylmesitylene, mp. 131°—179 

Phenyldixylylmethane, mp. 92°— 
Lig 

Benzylpentaethylbenzene, mp. 88° 
—177 

Methylhexadecylbenzenes, mp. 11°, 
27°—174 

Tricosane, mp. 48°—175 

Dibenzoylmesitylene, mp. 117°— 
138 


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FORMULA INDEX. 


Tolylpentadecyl ket., mp. 60°—137 
Fellic ac., mp. 120°—60 

Methyl behenolate, mp. 22°—118 
Laurone, mp. 69°—137 

Dilauryl] ale., mp. 75°—157 


C,, GROUP. 


Carbopetrocene, mp. 268°—181 

Benzerythrene, mp. 307°—181 

Triphenylbenzene, mp. 169°—179 

Octadecylbenzene, mp. 36°—175 

Dimethylhexadecylbenzene, mp. 
33°—175 

Tetracosane, mp. 51°—175 

Diacenaphthylidendione, mp. 295° 
—211 

Naphthalfluoresceine, mp. 308°— 
211 

Duryldibenzoyl, mp. 269°—140 

Hexaethyl mellitate, mp. 73°—119 

Paraphytosterine, mp. 149°—159 

Choleic ac., mp. 187°—67 

Cholic ac., mp. 195°—68 

Ethyl brassidate, mp. 29°—118 

Cerosine, mp. 82°—158 

Carnaubic ac., mp. 72°—55 

Lignoceric ac , mp. 80°—56 

Paraffinic ac., mp. 46°—53 

Carnauby] alc., mp. 68°—157 


C,, GROUP. 


Biphenylphenylenemethane, mp. 
162°—179 

Trixylylmethane, mp. 188°—180 

Trimethylhexadecylbenzene, mp. 
40°—175 

EKupittonic ac., mp. 200°—209 


(?) Arbutin, mp. 145°—97 


Cholanic ac., mp. 285°—72 
Isocholanic ac., mp. 245°—71 

Tolyl heptadecyl ket., mp. 67°—137 
Hyaenic ac., mp. 77°-—56 


C,, GROUP. 
Dibiphenyleneethylene, mp. 187°— 
180 . 


Tetraphenylethylene, mp. 221°— 
180 

Dibenzylbiphenyl, mp. 113°—178 

Tetraphenylethane, m. p. 209°— 
180 

Tetraphenylethylene dioxide, mp. 
315°—181 

Benzhydrol eth., mp. 111°—178 

Benzpinacoline, mp. 204°—180 

Benzopinacone, mp. 168°—159 

Ergosterine, mp. 154°—159 

Cholesterine, mp. 148°—158 

Paracholesterine, mp. 134°—158 

Phytosterine, mp. 182°—158 

Cerotic ac., mp. 78°—56 


C,, GROUP. 


Tritolylbenzene, mp. 171°—179 

Cerotene, mp. 57°—176 

Heptacosane, mp. 59°—176 

Benzaldinaphthyl oxide, mp. 189° 
—180 


C,,H,.0, 


Rutin, mp. a. 190°—209 
Isocholesterine, mp. 137°—158 
Myristone, mp. 76°—138 
Ceryl alc., mp. 79°—157 


C,, GROUP. 


Bianthranyl, mp. 300°—181 

Lepidene, mp. 175°—180 

Oxylepidenes, mp. 220°, 232°—210, 
139 

Anthrapinacone, mp. 182°—159 

Hydroxylepidene, mp. 254°—181 


C,,H,,O, Tetraphenylsuccinic ac., mp. 261° 


Cox H,,0, 
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Fi dohensee! anhyd., mp. 126°— 
Phesyltolyiene mp. 164°— 
Homccholedaees mp. 183°—159 
C,, GROUP. 
Lactarone, mp. 82°—138 
C,, GROUP. 


Tetratolylethylene, mp. phe et 
Melene, mp. 62°—176 
Chrysarobin, mp. 175°—208 
Picrotoxin, mp. 200°—100 
Santononic ac., mp. 215°—70 
Lithobilic ac., mp. 199°—68 
Melissic ac., mp. 90°—56 
Oxymelissic ac., mp. 95°—57 
Lanoceric ac., mp. 104°—58 
Myricyl ale., mp. 85°—158 
Coccerylic ale., mp. 102°—158 


C,, GROUP. 


Hentriacontane, mp. 68°—176 
Palmitone, mp. 83°—138 

Coceric ac., mp. 92°—57 

Palmitic anhyd., mp. 64°—129 
Dipalmitylcarbino 1, mp. 84°—158 


C,, GROUP. 
Dotriacontane, mp. 72°—176 


(?) Convolvulin, mp. 158°—98 


Ethylmelissate, mp. 72°—119 
Cetyl eth., mp. 55°—17 5 


C,, GROUP. 
Tetraxylylethylene, mp. 244°—18€ 


C,, GROUP. 
Pentriacontane, mp. 75°—176 
Stearone, mp. 88°—138 

C,, GROUP. 


Inulin, mp. 178°—31 
Stearic anhyd., mp. 73°—129 


C,, GROUP. 


Resorcinbenzeine,—213 ; 
Dibenzaltriacetophenones, mp. 1° ~ 
256°—139, 140 


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COLOR STANDARD.— SHEET A. 


DIRECTIONS FOR USE IN CHAPTER XIII, VOL. ! 

ulliken’s Method for the Identification of Pure Organic Compounds from colors 
will be replaced, in case of injury, by the publishers, John Wiley & Sons, 43-45 
ty cents —or thirty-five cents for either one of the two separate 


Eee 


This standard, which has been prepared for use in M 


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furnished by the courtesy of the Milton Bradley Company, 
tal money order for sixty cent: 
the work with which it is issued. 


East roth St., New York, upon receipt of a post 
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COLOR STANDARD.— — SHEET B. 


B. | Violet, v. 
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Red, eastR: Spe Ne Yellow-green, YG.| Blue, B. | Red-violet, RV 
Orange-red, OR. | Orange-yellow, OY.| Green, G.| Violet-blue, VB. 

Red-orange, RO. | Yellow, Y.| Blue-green, BG. Blue-violet, BY. 





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